CN102665774A

CN102665774A - Treated porous particles and methods of making and using the same

Info

Publication number: CN102665774A
Application number: CN2010800529833A
Authority: CN
Inventors: 布林达·B·巴德理; 莫塞斯·M·大卫; 折谷忠人; 荣浩鸣; 巴德理·维尔拉哈万
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 2009-11-23
Filing date: 2010-11-23
Publication date: 2012-09-12
Anticipated expiration: 2030-11-23
Also published as: WO2011063392A3; TW201134506A; CN102665893A; KR101851405B1; WO2011063372A3; CN102665894A; US20120219728A1; WO2011063392A2; WO2011063372A2; KR20120102087A; EP2504095A2; WO2011063370A3; JP5647260B2; JP5792738B2; JP2013511362A; US9078946B2; CN102665894B; KR20120112474A; BR112012012389A2; KR20120102088A

Abstract

A treated porous particle having an external surface and interior pore surfaces, with at least a portion of the external surface of the treated porous particle bearing a hydrophobic group, and with hydrophilic interior pore surfaces. The treated porous particles may be useful, for example, as desiccants. Absorbent articles, for example, diapers and sanitary napkins, and absorbent components of absorbent articles that include the treated porous particles are also disclosed.

Description

Treated porous granule and preparation thereof and method for using

CROSS-REFERENCE TO RELATED PATENT

The application requires the U.S. Provisional Application No.61/263 of submission on November 23rd, 2009, the U.S. Provisional Application No.61/263 that on November 23rd, 573 and 2009 submitted to, and 580 priority, these patent applications are incorporated this paper into way of reference in full.

Background technology

Some porous granule has been widely used in chemical field.For example, hydrophobic oxide material is widely used in different gas phases and liquid phase separation technology.Especially widely used example is a silica gel, and known silica gel can be used for multiple application, comprises chromatography, absorption and the purification of bioactive compound and pharmaceutical preparation and stablizing of multicomponent system.Yet the surface characteristic of native silicon dioxide is not always to be applicable to required application.Surface modification can be converted into hydrophobic group through (for example) hydrophilic silanol and realize that this conversion can reduce the affinity of improved silica with respect to water usually.Usually, it is hydrophobic that the silica gel hydrophobic treatment of knowing is intended to make outer surface and inner bore surface all to become.

In other technologies, use various technology to reduce the relative humidity in some environment.In personal care industries, during the disposable absorbent garment dress, know by the caused erythra problem that do not accommodate of excess humidity.Disposable absorbent garment (like incontinence with underwear, diaper and feminine hygiene) generally include the outer covering of the permeable body-side liner of liquid, liquid non-permeate and be arranged at body-side liner and outer covering between absorbent components.For fear of seepage, said absorption clothes must absorb liquid rapidly, on the surface of health, excessively compiles in body-side liner to avoid liquid.Absorb and any liquid of remaining all causes near the relative humidity the user skin to increase by clothes.User is perspired and also can be caused relative humidity to increase.Relative humidity height in the environment of contact user skin can cause discomfort or skin erythema (like diaper rash).

But the gas permeable material manufacturing of known employing permeate water steam absorbs the outer covering (being egative film) of clothes; So that the outside fresh air of clothes can exchange with the damp atmosphere near the environment user skin, and liquid can be evaporated in the external environment.Yet highly porous thin film but possibly be not enough to suppress the seepage in the goods as transpiration-cooled egative film is provided.Dehumidizer (like desiccant and/or wetting agent) is mixed in the component of disposable absorbent garment that the relative humidity of environment also is known near the user skin to reduce.

Although the development work of disposable absorbent garment has obtained progress, but still need to continue near the relative humidity with reducing user skin reliably.

Summary of the invention

The present invention relates to have hydrophobic group and treated porous granule of hydrophilic inside on the outer surface and preparation method thereof.Treated porous granule can be used to control the desiccant of the humidity in the absorbent article environment as (for example).Usually comprise super-absorbent polymer (SAP) and/or wood pulp in the core area of absorbent article (like sanitary towel and health diaper), to absorb and the maintenance fluid.Under the situation that has SAP or wood pulp, treated particle disclosed herein demonstrate reduce with absorbent article user skin near the ability of the humidity in the environment like the environmental classes.

In one aspect, the present invention provides the treated porous granule that comprises outer surface and inner bore surface, and the major part at least of the outer surface of wherein treated porous granule comprises hydrophobic group, and wherein inner bore surface is undressed basically.In certain embodiments, hydrophobic group comprises at least one in the alkyl or aryl, and wherein alkyl and aryl are randomly replaced by fluorine separately.In certain embodiments, treated porous granule is treated desiccant particles.In certain embodiments, treated porous granule is treated silica gel particle, treated montmorillonitic clay particle, treated zeolite particles, treated molecular sieve or treated activated carbon particles.In certain embodiments, treated porous granule is treated silica gel particle or treated activated carbon particles.In certain embodiments, hydrophobic group comprise have alkyl, the siloxanes of aryl or their combination.In certain embodiments, treated porous granule is a silica gel particle, and as confirming through the x-ray photoelectron power spectrum, the as many as 50 angstroms depth places of this silica gel particle outer surface have the silicon atom of maximum 5 atom %.

The present invention also provides the treated porous granule that comprises outer surface and inner bore surface; At least a portion of the outer surface of wherein treated porous granule comprises hydrophobic group; Said hydrophobic group comprises at least one in the alkyl or aryl; Wherein said alkyl and aryl are replaced by fluorine, and wherein inner bore surface for part is hydrophilic at least.In certain embodiments, treated porous granule is treated desiccant particles.In certain embodiments, treated porous granule is treated silica gel particle, treated montmorillonitic clay particle, treated molecular sieve or treated activated carbon particles.In certain embodiments, hydrophobic group comprise have alkyl, the siloxanes of aryl or their combination.In certain embodiments, treated porous granule is a silica gel particle, and as confirming through the x-ray photoelectron power spectrum, the as many as 50 angstroms depth places of this silica gel particle outer surface have the silicon atom of maximum 5 atom %.

The present invention also provides a plurality of particles that comprise treated porous granule.In certain embodiments, said a plurality of particle also comprises undressed desiccant particles (like silica gel, montmorillonitic clay, molecular sieve, zeolite or active carbon).In certain embodiments, said a plurality of particle does not contain the particle that its outer surface and inner bore surface are all handled with hydrophobic group basically.In certain embodiments, said a plurality of particles also comprise absorbing particle or fiber, and said absorbing particle or fiber comprise at least one in super-absorbent polymer, hydrophilic nonwoven cloth or the wood pulp.

In some embodiment of treated particle according to the present invention or said a plurality of particles; When treated porous granule is sprayed onto on the water surface when forming monolayer; At least 75% particle floats on the surface, and treated porous granule absorbs the steam of its weight at least 20% after under 30 ℃ and 50% relative humidity, keeping 24 hours.In in these embodiment some, it is waterborne that the treated porous granule of a gram is spread 10 milliliters (mL) being contained in the 20mL bottle.In certain embodiments, under 30 ℃ and 80% relative humidity, the steam absorbance of this particle be do not comprise said hydrophobic group a plurality of contrast particles the steam absorbance at least 60%.In certain embodiments, when at least a portion of said a plurality of particles is exposed to when liquid, aqueous, compare with a plurality of contrast particles that do not comprise hydrophobic group, said a plurality of particles can reduce relative humidity to a greater degree.

On the other hand, the present invention provides the bonded absorbent components that comprises absorbing material and a plurality of treated porous granule disclosed herein.In certain embodiments, absorbing material is at least one in wood pulp, super-absorbent polymer or the acrylic acid series foam.

On the other hand, the present invention provides the absorbent article that comprises the absorbent components described in above-mentioned any aspect or the embodiment, or comprises the absorbent article of a plurality of particles described in above-mentioned any aspect or the embodiment.In certain embodiments, absorbent article is oxter liner, breast pad, antiperspirant pad, shoe pad, wound dressing, mattress or liner, diaper or sanitary towel.In certain embodiments, absorbent article comprise the egative film of liquid permeable topsheet, liquid non-permeate and be arranged at top flat and egative film between absorbent components and/or above-mentioned a plurality of particle.

On the other hand, the present invention provides the purposes of treated porous granule (or a plurality of particle disclosed herein) disclosed herein as desiccant.In certain embodiments, desiccant be exposed to liquid, aqueous in.In certain embodiments, desiccant is used for absorbent article.

On the other hand, the present invention provides drying means, and said method comprises treated porous granule disclosed herein (or a plurality of particle disclosed herein) is placed wet environment that wherein treated porous granule absorbs water from wet environment.In certain embodiments, water is steam.In certain embodiments, treated porous granule contacts with liquid, aqueous.In certain embodiments, wet environment is arranged in absorbent article (on the health like the wearer).

On the other hand, the present invention provides the purposes of treated porous granule (or a plurality of particle disclosed herein) disclosed herein as odor control agent.In certain embodiments, odor control agent be exposed to liquid, aqueous in.In certain embodiments, odor control agent is used for absorbent article.In certain embodiments, treated porous granule is treated activated carbon particles.

On the other hand; The present invention provides the method for control abnormal smells from the patient; Said method comprises treated porous granule disclosed herein (or a plurality of particle disclosed herein) is placed the environment with a certain amount of stink agent that wherein treated porous granule can reduce the amount of stink agent in the environment.In certain embodiments, treated porous granule contacts with liquid, aqueous.In certain embodiments, environment is arranged in absorbent article (on the health like the wearer).In certain embodiments, treated porous granule is treated activated carbon particles.

On the other hand; The present invention provides the method for preparation according to the described treated porous granule of above-mentioned arbitrary embodiment; Said method is included in the inner bore surface that makes porous granule and keeps the undressed basically while, handles the outer surface of porous granule with water-repelling agent.In certain embodiments, have only the outer surface of porous granule just to handle with water-repelling agent.

According to the present invention and/or the outer surface that can be used for putting into practice treated porous granule of the present invention for part is hydrophobic at least.Usually, treated porous granule is to absorb aqueous water (liquid, aqueous with other) than much lower speed of similar undressed porous granule or much lower degree.Therefore, the hydrophobic group on the outer surface helps to repel liquid, aqueous.Basically hydrophilic inner bore surface absorbs steam.

The relative humidity of environment is known near wearer's skin to reduce though desiccant (like silica gel) is mixed in the component of absorbent article; But when these desiccant are exposed to when liquid, aqueous; Their effectiveness can go down or is inconsistent, and tends to cause the wet and slippery or sticky sense of absorbent article.It is known that desiccant is encapsulated in the pouch of being processed by following material, and this material can allow vapor permeation and repel liquid, aqueous material (microporous membrane or the particle-filled film processed as being separated through thermic).Place absorbent article possibly need special Technology this type of pouch, and possibly be worthless therefore.Treated porous granule disclosed herein usually repels liquid, aqueous, and demonstrates more more lasting and reduce near the ability of the relative humidity wearer's skin reliably than undressed desiccant particles in the present invention.Can they be added in the absorbent article, and need not use the physical isolation of pouch or other troubles technological.

Similarly, when being exposed to when liquid, aqueous, the effectiveness of odor control agent (like active carbon and silica gel) can go down or is inconsistent.Treated porous granule disclosed herein usually repels liquid, aqueous, and demonstrates when moistening the ability that reduces abnormal smells from the patient than undressed desiccant particles more reliably in the present invention.They also can add absorbent article under the situation of the physical isolation technology that need not use pouch or other troubles.

Definition

In present patent application:

Such as " one " and " said " such term is not to be intended to refer to single entity, but comprises general category, and object lesson wherein can be used to illustrate.Term " one " and " said " can exchange with term " at least one " and use.

The phrase of the tabulation of two or more projects of followed " at least one " is meant the combination in any of two or more projects in any and the tabulation of tabulation item.

" hydrophilic " described can be by the surface of liquid, aqueous (that is, wrapping aqueous liquid) moistening of contact surface.Wettability can be measured through liquid contact angle from the teeth outwards.Usually, when water contact angle from the teeth outwards is during less than 90 °, the surface is hydrophilic.

" hydrophobic group " described and can be made the surface not by the functional group of liquid, aqueous (that is, wrapping aqueous liquid) moistening of contact surface.Usually, when water contact angle from the teeth outwards is during greater than 90 °, the surface is hydrophobic.

" at least a portion of outer surface " and " major part at least of outer surface " can comprise that hydrophobic group evenly or unevenly is distributed on the outer surface of particle.In certain embodiments, hydrophobic group is evenly distributed on the outer surface of particle.In certain embodiments, the whole outer surface of particle is covered by hydrophobic group.

" desiccant " is meant the material that can absorb moisture from the ambient atmosphere environment.Can water or steam be absorbed in the loose structure through the Physical Absorption mode at this used desiccant.

Term " absorbent components " is meant the component that is used as the main absorbent components of absorbent article usually, the for example absorbent cores of absorbent article.It also comprises the absorbent components that plays second top flat of wicking or storage effect such as as herein described.Yet term " absorbent components " has been got rid of usually only as the top flat of absorbent article or the component of egative film.

" disposable " is generally understood as and means limited things of operating period before the ability of carrying out its expectation function is exhausted.With regard to clothes, " disposable " clothes is not configured to stand washing usually.

" moisture " means and comprises water.Biofluid contained in term " aqueous fluid ".

" alkyl " and prefix " alkane " comprise straight chain and branched group and cyclic group.Except as otherwise noted, otherwise the alkyl among this paper has 20 carbon atoms of as many as.Cyclic group can be monocycle or polycyclic, in certain embodiments, has 3 to 10 ring carbon atoms." alkylidene " is the bivalent form of " alkyl ".

Term " fluoroalkyl " comprises that wherein all c h bonds are all by the substituted straight chain of C-F key, side chain and/or cyclic alkyl group; And wherein having hydrogen or chlorine atom but not the group of fluorine atom, precondition is to have hydrogen atom of as many as or chlorine atom for per two carbon atoms.In some embodiment of fluoroalkyl, when having at least one hydrogen or chlorine, said fluoroalkyl comprises at least one trifluoromethyl.Term " perfluoroalkyl " comprises straight chain, side chain and/or cyclic alkyl, and wherein all c h bonds are all replaced by the C-F key.

" aryl alkylene " is meant " alkylidene " part that connects aryl.

Comprise carbocyclic ring type aromatic ring or member ring systems at this used term " aryl ", for example have 1,2 or 3 ring and choose wantonly and in ring, comprise at least one hetero atom (like O, S or N).The example of aryl comprises phenyl, naphthyl, xenyl, fluorenyl and furyl, thienyl, pyridine radicals, quinolyl, isoquinolyl, indyl, isoindolyl, triazolyl, pyrrole radicals, tetrazole radical, imidazole radicals, pyrazolyl 、 oxazolyl and thiazolyl.

" arlydene " is the bivalent form of " aryl " that as above define.

" alkyl arylene " is meant " arlydene " part that connects alkyl.

" Cement Composite Treated by Plasma " is meant the process of in the atmosphere that porous granule exists, using high-frequency electric field or magnetic field to produce the free radical of specific gas.Modification is carried out on the surface of radical pair porous granule.Term " Cement Composite Treated by Plasma " can be contained " plasma-deposited ", and the film that is wherein formed by plasma is deposited at least a portion on surface, and is attached to the surface through covalent bond usually.

Except as otherwise noted, otherwise all numerical rangies include their end points and the non integer value between the end points.

Description of drawings

With reference to below in conjunction with the detailed description of accompanying drawing to a plurality of embodiment of the present invention, can more fully understand the present invention, wherein:

Fig. 1 is the sketch map according to the treated porous granule of the method for the treated porous granule of the preparation of some embodiments of the present invention and gained;

Fig. 2 A is the schematic plan of device that is used for measuring the relative humidity of the absorbent article described in instance;

Fig. 2 B is the schematic side elevation of device that is used for measuring the relative humidity of the absorbent article described in instance;

Fig. 3 A is the schematic side elevation that is used for handling in vapor phase the device of porous granule according to some embodiments of the present invention, and what said processing was adopted is the illustrative methods of the treated porous granule of preparation;

Fig. 3 B is the particle agitator perspective schematic view partly of the device of Fig. 3 A;

Fig. 3 C is a schematic side elevation of handling the used another kind of exemplary means of porous granule according to use first vapor phase of some embodiments of the present invention and second vapor phase, and what said processing was adopted is another illustrative methods of the treated porous granule of preparation;

Fig. 4 A-4D is the sketch map according to the treated porous granule of the method for the treated porous granule of the preparation of some embodiments of the present invention and gained; And

Fig. 5 is the schematic, exploded according to Exemplary absorbent articles of the present invention.

The specific embodiment

Particle

Fig. 1 illustrates processing porous granule 1 and the sketch map of treated porous granule 5 according to some embodiments of the invention.In the illustrated embodiment, porous granule 1 has hydrophilic outer surface and hydrophilic inner bore surface.In this embodiment, (be hydrophilic OH), hydroxyl is illustrated in the drawings on the outer surface of the circle of representing porous granule 1 and is inner owing to having a plurality of hydroxyls for hydrophilic outer surface and inner bore surface.When using water-repelling agent and handling porous granule 1 according to the method for the invention, form treated porous granule 5.In the illustrated embodiment, treated porous granule 5 has hydrophobic outer surface, lip-deep a plurality of hydrophobic group (R) expression beyond this hydrophobic outer surface.Yet the inner bore surface of treated porous granule 5 still keeps hydrophilic, and this inner bore surface is also to represent at the hydroxyl shown in the circle inside of the treated porous granule 5 of representative.

In any embodiment of treated porous granule 5 according to the present invention, at least a portion of the outer surface of said treated porous granule comprises hydrophobic group R.Exemplary R base comprises alkyl and fluoro-alkyl, and said alkyl and fluoro-alkyl have 20,18,15,12,10 or 8 carbon atoms of as many as (as in the scope of 1 to 20,1 to 15,1 to 10,1 to 5 or 1 to 3 carbon atoms).Other examples of R base comprise aryl, aryl alkylene or alkyl arylene, and each in the said group all can be by one or more fluorine-based replacements.In certain embodiments, the R base comprises at least one in methyl, trifluoromethyl, difluoromethyl or the fluoro methyl.In certain embodiments, hydrophobic group R comprises siloxanes, and said siloxanes has alkyl, aryl, aryl alkylene (like benzyl), alkyl arylene or their combination.In in these embodiment some, treated porous granule 5 is treated silica gel particles.Alkyl on the siloxanes has 20,18,15,12,10 or 8 carbon atoms of as many as (as in the scope of 1 to 20,1 to 15,1 to 10,1 to 5 or 1 to 3 carbon atoms), and can be randomly by one or more fluorine-based replacements.

Usually, the major part of outer surface region (as greater than 50% or at least 51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%) is covered by hydrophobic group.In certain embodiments, the major part of outer surface (like at least 90%, 95%, 96%, 97%, 98% or 99% as many as 100%) comprises hydrophobic group.The technology that is used to analyze the particle external surface coverage rate is well known in the art (like infrared, Raman and NMR spectrum); Referring to like L.A.Belyakova et al.; Colloids and SurfacesA:Physicochemical and Engineering Aspects, 154 (1999), pp.285-294 (people such as L.A.Belyakova; " colloid and surface; A collects: physical chemistry problem and engineering problem ", the 154th volume 285-294 page or leaf, 1999).The outer surface of particle also can use chemical analysis of the electron spectrum method (ESCA) to analyze.ESCA can be used for various elements atomic percentage on the recording surface.The result depends on (for example) lip-deep specific hydrophobic group and they is applied to the method on surface.In certain embodiments, the major part that comprises the outer surface of hydrophobic group is meant as not having the element of forming porous granule on the surface of confirming through ESCA.(is the embodiment of treated silica gel particle like, wherein treated porous granule 5) in certain embodiments, as confirming through the x-ray photoelectron power spectrum, the as many as 50 angstroms depth places of outer surface are silicon atoms not.The outer surface of particle also can use flight time secondary ion mass spectrometry (TOF-SIMS) to analyze.TOF-SIMS can be used for detecting the lip-deep chemical composition that common depth bounds is 5 to 20 dusts.The result depends on (for example) lip-deep specific hydrophobic group and they is applied to the method on surface.Use SIMS to carry out relative quantification and be fine, pays close attention to the ratio of quality counting and benchmark ion counting usually through getting or institute's quality of paying close attention to is counted and always the ratio counted of spectrum integral carry out.

Usually, when treated porous granule 5 floated on the surface, the major part of the outer surface of treated porous granule 5 disclosed herein comprised hydrophobic group.When the surface tension of liquid enough high when being equilibrated at the interface particle gravity of gas/liquid, on particle is expressed as and floats on the surface.When treated porous granule 5 according to the present invention is sprayed onto on the water surface, the wettability of treated porous granule 5 maybe with the particle used time correlation of sinking.In certain embodiments, treated porous granule 5 is retained on the water surface indefinitely.In certain embodiments, treated porous granule 5 is retained on the water surface at least 8 hours, 6 hours, 4 hours, 2 hours or 30 minutes.The floating granules method is well known in the art the technology of the surface wettability that is used to assess particle; (referring to like M.Lazghab et al., Powder Technology, 157 (2005), p.83 people such as (, " powder technology ", the 83rd page of the 157th volume, 2005 years) M.Lazghab).Assess hydrophobicity through treated porous granule 5 being sprayed on the water surface according to the outer surface of a plurality of treated porous granules 5 of the present invention to form monolayer.Usually, at least 75% the particle of (in certain embodiments 80%, 85%, 90% or at least 95%) floats on the surface.In certain embodiments, this assessment can be carried out through following method: the treated porous granule of a gram is placed on 10 milliliters of (mL) waters surface that are contained in the 20mL bottle and observes on whether particle float on the surface.When rocking the bottle that treated particle and water are housed, particle can be reunited usually.As time goes on, the particle of reunion can scatter usually, and in water, floats once more.During undressed hydrocolloid particle in rocking water, do not observe this type of block thing that forms usually.On the contrary, the common submerged of undressed hydrocolloid particle.

Be not that all hydrophobic treatment all can form the particle that floats on the surface.For example, hydrolysis possibly take place in some hydrophobic treatment (as when surface hydroxyl is replaced by fluorine through Cement Composite Treated by Plasma) when the contact aqueous water.Observe at present, use NF ₃The particles of Cement Composite Treated by Plasma can not float on the surface, and understands submerged on the contrary.Hydrophobic treatment provided by the invention is firm, and can hydrolysis when placing particle on the water surface.

Hydrophobicity according to treated porous granule 5 of the present invention also can (for example) use the contact angle measurement method to assess, and this method adopts technology as known in the art that single particle or large quantities of particle are measured.In certain embodiments, the contact angle of little water droplet and treated porous granule 5 at least 120,110,100 or 95 degree (as, scope from 90 to 100 degree, 95 to 110 degree, 100 to 115 degree, 110 to 130 degree or 115 to 125 degree).

In any embodiment of treated porous granule 5 according to the present invention, the inner bore surface of treated porous granule 5 is for part is hydrophilic at least.In certain embodiments, when the inner bore surface of treated porous granule 5 has hydrophilic functional groups, they are expressed as hydrophilic.According to the character of particle, hydrophilic functional groups generally includes hydroxyl, silanol group or other metallic oxide groups.In certain embodiments; When porous granule 1 has the inner bore surface that comprises hydroxyl or silanol group; Treated porous granule 5 has at least 50%, 60%, 70%, 75%, 80%, 85% or 90% hydroxyl or silanol group, and these groups just are present in the porous granule 1 before processing.The method of the inner bore surface of assessment porous granule is well known in the art.For example, use absorption techniques (as using methanol, ethanol, water, benzene or nitrogen) usually.Because the surface area of the big percentage ratio in the porous granule is arranged in inner bore surface, therefore when the wettability modification of inner bore surface, can cause absorption to change a lot usually.For example, as use conventional absorption techniques mensuration, treated porous granule 5 at least 90%, 95%, 96%, 97% or 98% hydroxyl or silanol group just are present in before processing in the porous granule 1, inner bore surface can be expressed as " undressed basically ".Porous granule also can be a section, and their inner chemical compositions use above-mentioned ESCA or TOF-SIMS to analyze.In certain embodiments, use these technology to observe minute quantity even do not have hydrophobic group in treated porous granule inside.In these embodiment, inner bore surface is expressed as " undressed basically ".In certain embodiments, the inner bore surface of treated porous granule disclosed herein has minute quantity even does not have alkyl or aryl, and said alkyl or aryl is randomly replaced by fluorine, as TOF-SIMS confirms.With regard to TOF-SIMS, hydrophobic and hydrophilic functional groups are carried out relative quantification be fine, the quality counting through getting hydrophobic group carries out with the ratio of the counting of hydrophilic group usually.Can be with comparing from the counting ratio of outer surface and counting ratio from inner surface.

In certain embodiments, treated porous granule 5 disclosed herein is at the steam of 24 hours its weight at least 20% of post-absorption of 30 ℃ and 50% relative humidity held (in certain embodiments at least 22%, 25%, 28%, 30% or 32%).In general, this is absorbed in the humidity cabinet under the situation that does not have aqueous water and carries out, and the weight of operational analysis balance weighing particle.The amount of porous granule 1 or treated porous granule 5 absorbable steam disclosed herein depends on the type of particle.For example, report that usually silica gel particle absorbs the water of its weight about 40%.In certain embodiments, under 30 ℃ and 80% relative humidity, the steam absorbance of treated porous granule be a plurality of contrast particles that do not comprise hydrophobic group the steam absorbance at least 50%, 55%, 60%, 65%, 70%, 75% or 80%.In certain embodiments; When the inner surface of treated porous granule the steam absorbance under 30 ℃ and 80% relative humidity be a plurality of contrast particles that do not comprise hydrophobic group the steam absorbance at least 60%, 65%, 70%, 75% or 80% the time, this inner surface is expressed as " undressed basically ".A plurality of contrast particles that do not comprise hydrophobic group are meant identical with said a plurality of treated particles but without a plurality of particles of hydrophobic treatment.For example, before these type of a plurality of contrast particles were processed, its size was identical with said a plurality of treated particles with pore-size distribution, and chemical composition is identical with treated porous granule.

Treated porous granule 5 according to the present invention comprises treated silica gel particle, treated zeolite particles, treated montmorillonitic clay particle, treated molecular sieve and treated active carbon.The mean particle size range of treated porous granule can for 0.075 millimeter (mm) to 10mm (as from 0.1mm to 10mm, 0.5mm to 5mm or 0.5mm to 1mm).When treated porous granule is used as desiccant, must be enough to allow hydrone to get into as long as the hole is big, mean pore sizes just can have difference.In certain embodiments, the scope of the mean pore sizes of endoporus be 1 nanometer (nm) to 10nm (as, 2nm to 3nm, 2nm to 7nm, 4nm to 7nm, 8nm to 10nm or 4nm to 10nm).In certain embodiments, treated porous granule has bimodal loose structure, and its mesopore has two kinds of different mean pore sizes of any person in listed scope.Porous granule 1 before handling can derive from multiple be purchased the source (like AGM Container Controls, Inc. (Tucson, AZ), International Silica Gel Co., LTD (Shandong, China) and SIGMA-ALDRICH (St.Louis, MO)).In certain embodiments, treated porous granule can comprise color indicator (like cobaltous chloride), changes with Show Color when absorbing moisture.

Though the hydrophobic treatment of silica gel particle is known, to be intended to make outer surface and inner bore surface all to become hydrophobic for this hydrophobic treatment usually.The treated particle of part can derive from outer surface and inner bore surface all are treated to hydrophobic method, if and if outer surface do not covered or hydrophobic group hydrolysis when contact with water by the hydrophobic group of q.s, then said particle maybe not can float in the water.In addition, hydrophobic if the major part of outer surface and inner surface is prepared as, then the treated particle of this type of part maybe not can absorb the water of (for example) its weight at least 20%.Usually, known before this solvent and the steam technology that is used for the silica gel particle hydrophobic treatment can not allow to be reflected at the some place that inner bore surface is not processed easily and stop.In addition, as the inner bore surface and the outer surface of the radio frequency carbon tetrafluoride Cement Composite Treated by Plasma silica gel of individual processing agent; Referring to like K.Furukawa et al., Journal of Materials Science Letters, 19 (2000), pp.1545-1547 people such as (, " material science magazine wall bulletin ", the 19th volume 1545-1547 page or leaf, 2000 years) K.Furukawa.

By contrast, comprise hydrophilic inner bore surface according to treated porous granule of the present invention and/or prepared in accordance with the present invention, this hydrophilic inner bore surface makes treated particle can be used as (for example) desiccant.Its outer surface and inner bore surface are hydrophobic hydrophobic silicone can not be used as desiccant.In certain embodiments, a plurality of treated porous granules comprise that its outer surface and inner bore surface are all handled with hydrophobic group less than the particle of 25% (in certain embodiments, less than 20%, 15%, 10%, 5%, 4%, 3%, 2% or 1%).Said a plurality of treated porous granule can be described as and is substantially free of particle, and its outer surface and inner bore surface are all handled with hydrophobic group.

The particle preparation method

Preparation comprises that according to the method for the treated porous granule 5 among above-mentioned any embodiment the inner bore surface that makes porous granule 1 keeps the undressed basically while, handles the outer surface of porous granule 1 with water-repelling agent." undressed basically " has implication same as described above.In certain embodiments, have only the outer surface of porous granule 1 just to handle with water-repelling agent.

The plasma processing method of porous material provides among 419 (people such as David) at United States Patent(USP) No. 6,878.In addition, the method and apparatus that is used for plasma treatment particles is at United States Patent(USP) No. 6,015, and 597 (David) and No.6 provide among 197,120 (David), and the disclosure of these patents is all incorporated this paper into way of reference.In certain embodiments, the method for the treated porous granule of preparation comprises through the plasma-deposited layer that comprises silicon, hydrogen and carbon that at least a portion outer surface of porous granule, forms.The step that forms this layer can be carried out through the gas that ionization includes organic silicon compound, and said organo-silicon compound are selected from alkyl silane, alkoxy silane, alkylidene polysilane, alkyl polysilane, thiazolinyl silane, aryl-silane and their combination.Exemplary alkyl silane comprises tetramethylsilane, methyl-monosilane, dimethylsilane, diethylsilane, diethylmethyl silane, propyl silane, trimethyl silane and ethylsilane.Exemplary alkoxy silane and siloxanes comprise tetraethyl orthosilicate (TEOS) and tetramethyl-ring tetrasiloxane (TMCTS).Exemplary alkylidene polysilane comprises two silicon methylmethanes, two (methyl silicon methylene) methane, 1; 2-two silicon methyl ethane, 1; 2-two (methyl silicon methylene) ethane, 2,2-two silicon methylpropanes, dimethyl two silicon methylene ethane, dimethyl two silicon methylene propane, tetramethyl two silicon methine ethane and tetramethyl two silicon methine propane.Exemplary alkenyl groups silane comprises thiazolinyl methyl-monosilane and divinyl dimethylsilane.Exemplary aryl-silane comprises phenyl silane, phenyl dimethylsilane and phenyl-trimethylsilicane.The exemplary alkyl polysilane comprises 1,1,2,2-tetramethyl disilane, hexamethyldisilane, 1,1,2,2,3,3-hexamethyl three silane and 1,1,2,3,3-pentamethyl three silane.The substituent group of organo-silicon compound can be the group of for example amino, hydroxyl and/or halogen (like fluorine, bromine, chlorine), but they are normally unsubstituted.In certain embodiments, organo-silicon compound have at least one c h bond, and this c h bond can be sp3, sp2 or sp c h bond.Usually, organosilicon has a plurality of c h bonds, for example at least 2, at least 3, at least 5, at least 9 and/or even at least 12 c h bonds, perhaps more.Common available organo-silicon compound have enough vapour pressures under the plasma process conditions that forms plasma.

In some embodiment of the method for the treated porous granule of preparation, said method also comprise with fluorochemical (as through Cement Composite Treated by Plasma or deposition) pack processing is siliceous, hydrogen and carbon layer at least a portion.Fluorochemical is hydrocarbon normally, and wherein at least some in the hydrogen atom are replaced by fluorine atom.Fluorochemical can be straight chain, side chain or cyclic, and can be fully saturated or part is undersaturated.Fluorochemical comprises maximum 5 carbon atoms (as maximum 4,3 or 2) usually.For plasma-deposited, fluorochemical comprises at least 2 or 3 carbon atoms usually.In certain embodiments, fluorochemical is fluoridized (that is, all c h bonds is all replaced by the C-F key).In certain embodiments, fluorochemical is selected from perfluoropropane, carbon tetrafluoride, fluoroform, difluoromethane, pentafluoroethane, perfluoropropene, perfluorinated butane and perfluorobuttene and their combination.

In certain embodiments, Cement Composite Treated by Plasma is accomplished in two steps.For example;, the method for the treated porous granule of preparation forms the layer that comprises silicon, hydrogen and carbon on comprising through plasma-deposited at least a portion outer surface at porous granule; And during at least a portion of the layer through plasma-deposited, hydrogen siliceous and carbon with the fluorochemical pack processing; First step Cement Composite Treated by Plasma is usually included under the vacuum and handles porous granule 1 with gas (like above-mentioned organo-silicon compound), and lights plasma.Although have no intention to accept the constraint of opinion, it is believed that when gas is (for example) tetramethylsilane (TMS) layer of the involved methyl of outer surface of treated porous granule covers, this methyl provides hydrophobic outer surface.When using second to go on foot Cement Composite Treated by Plasma, be usually included under the vacuum and handle said treated porous granule 5, and light plasma with second gas (like above-mentioned fluorochemical).Although have no intention to accept the constraint of opinion, it is believed that second goes on foot and will replace more lip-deep hydrogen of porous granule (like c h bond) with fluorine, to generate CF, CF from the teeth outwards ₂Or CF ₃Group.If use deposition fluorochemical plasma (as, wherein fluorochemical has at least 2 or 3 carbon atoms), it is believed that then the layer that comprises fluorocarbon forms from the teeth outwards.The carrying out time of each in said two treatment steps can be (for example) at least 5 minutes, 10 minutes, 20 minutes, 30 minutes, 45 minutes or 60 minutes or longer altogether.Usually, Cement Composite Treated by Plasma is carried out under the pressure of maximum about 1000,750,500,250,100 or 75 millitorrs (133,100,67,33,13 or 10Pa).

Cement Composite Treated by Plasma need be mixed porous granule 1 usually, so that be exposed to the amount maximization of the exterior surface area of plasma.When Cement Composite Treated by Plasma is carried out with laboratory scale, can manually mix.For example, in above-mentioned two-step technology, each step all can be interrupted repeatedly (as 2,3 or 4 times) to stir porous granule.And then introducing gas, and light plasma once more.In fairly large processing, can use (for example) mixing paddle to mix, said mixing paddle can rotate during handling continuously.

Using the plasma preparation also to comprise usually according to the method for treated porous granule of the present invention provides the reative cell with capacitive coupled system, this capacitive coupled system to comprise at least one ground electrode and at least one electrode by the radio frequency source power supply; Generation comprises the plasma of reactant in reative cell, thereby causes forming of at least one in said electrode of ion sheath on every side; And the definite position of a plurality of porous granules in ion sheath.In certain embodiments, said method also comprises by following mode and stirs said a plurality of porous granule: make their outer surface be exposed to the reactant in the plasma.

In above-mentioned Cement Composite Treated by Plasma, plasma (like silane plasma or fluoro plasma) can comprise other gas components, and for example nitrogen or ammonia become hydrophobic as long as said gas component does not suppress outer surface.Therefore, used therein among the embodiment of gas, term " gas " is meant the mixture of unification compound or two kinds or more compounds.

Cement Composite Treated by Plasma can form the treated porous granule with unique texture, because it only handles the outer surface of particle usually.Usually, for treated porous granule disclosed herein, the aperture in the scope of as many as tens nanometer, and the mean free path of reactant in the plasma (that is, material with another kind of material collision before the average distance of advancing) for being not less than 20 microns.In addition, plasma-deposited method can form the hydrophobic substance layer from the teeth outwards.The method of in above-mentioned any embodiment, describing all can provide the treated silica gel particle that comprises outer surface and inner bore surface; Confirm that wherein as through the x-ray photoelectron power spectrum the as many as 50 angstroms depth places of outer surface have the silicon atom of maximum 5 (as 4,3,2.5,2 or 1) atom %.In in these embodiment some, outer surface is silicon atoms not.In certain embodiments, as confirming that through the x-ray photoelectron power spectrum the treated porous granule that is prepared by Cement Composite Treated by Plasma has the fluorine atom of at least 10,20,30 or 40 atom % at its outer surface 50 angstroms depth places.In certain embodiments, as confirming that through the x-ray photoelectron power spectrum the treated porous granule that is prepared by Cement Composite Treated by Plasma has the oxygen atom less than 20,15,10 or 5 atom % at its outer surface 50 angstroms depth places.In any of these embodiment, inner bore surface is usually all for part is hydrophilic at least.

In certain embodiments; Preparation all comprises according to the method for the treated porous granule 5 of any embodiment of above-mentioned treated porous granule porous granule 1 is exposed in steam, methanol vapor or the ethanol steam at least one, subsequently porous granule is exposed in second steam that comprises reactive organic silane compound.This method is called " second method " hereinafter.Handling silica surface with reactive organic silane compound is known in (for example) quasiconductor and printing industry.In semicon industry, silicon chip is used the dichlorodimethylsilane steam treated.In printer toner cartridge, inner bore surface and outer surface all are used as lubricant with the treated silica gel particle of dichlorodimethylsilane.Verified in the assessment of atresia silicon dioxide granule, the reaction between dichlorodimethylsilane and the silica surface is owing to the existence of surface water strengthens.In some embodiment of method disclosed herein; Be surprised to find that the reaction between vapor-phase reaction organic silicon hydride compounds and the porous granule 1 preferentially mixes hydrophobic group on the outer surface of porous granule, and do not influenced the drying capacity of particle inner bore surface.

In the first step of second method of the treated porous granule 5 of preparation, porous granule 1 is exposed in steam, ethanol steam or the methanol vapor at least one.This exposure can ambient pressure (as; In the humidity cabinet of for example 50% to 95% relative humidity) or decompression (as; Use the device 300 shown in Fig. 3 A and Fig. 3 B) under and ambient temperature or high temperature (as, in the scope of 25 ℃ to 40 ℃ or 25 ℃ to 35 ℃) under carry out.Never hope that the angle receive theory sets out, it is believed that in certain embodiments at least a portion of steam, methanol vapor or ethanol steam is condensed at least a portion in a plurality of holes of porous granule, thus closed interior hole surface at least in part.

In second step of second method for preparing treated porous granule 5, porous granule 1 is exposed in second steam that comprises reactive organic silane compound.This expose usually decompression (as, in 0.5 holder to 150 holder (67Pa to 2 * 10 ⁴Pa) in the scope) under carry out, and can ambient temperature or high temperature (as, in the scope of 25 ℃ to 40 ℃ or 25 ℃ to 35 ℃) under carry out.In certain embodiments, the pressure of the steam that comprises reactive organic silane compound when the contact particle is 400Pa at least, 650Pa, 1000Pa, 1300Pa or 10000Pa at least.Be surprised to find that when the pressure of the steam that comprises reactive organic silane compound during particle is improved as the performance of desiccant (as when being exposed to when liquid, aqueous) for 1000Pa (1300Pa according to appointment) at least.Although have no intention to accept the constraint of opinion, it is believed that the pressure of 1000Pa at least is diffused into reactive organic silane compound degree in the hole of particle and reduces to minimumly, rest on the outer surface so that handle.When the vapour pressure of reactive organic silane compound is during greater than 10 holders (1300Pa), can use the operation pressure of 10 holders (1300Pa) easily; Usually, inner steam, ethanol steam or methanol vapor can not discharged under this pressure in the hole of particle.

In the above-mentioned first step or in second step, said method can also comprise by following mode and stirs a plurality of porous granules: their outer surface is exposed in the steam or second steam at least one.

Said first and second steps can use the device 300 shown in (for example) Fig. 3 A and Fig. 3 B to carry out.Shown in Fig. 3 A, can use two liquid keeper assemblies 360 (is used for reactive organic silane compound, and is used for water) with delivery of vapor to the vacuum chamber 340 that is connected with vacuum pump 350.Vacuum chamber is generally and can be evacuated to is at most 10 ^-6Holder (10 ^-4The hollow circular cylinder of background pressure Pa).Each liquid keeper assembly all can comprise the compatible glass tubing 362,364 of the vacuum of sealing at one end, and the open/close connection valve 366 of control vapor source.Carry out in like above-mentioned humidity cabinet (for example) if be exposed to steam, then need not use one (it comprises pipe 362) in two liquid keeper assemblies.The inside of vacuum chamber 340 is the particle agitators 320 with vapour inlet port 330.Can (for example) service property (quality) flow controller or needle valve second steam that comprises reactive organic silane compound that gets in the humidity cabinet 340 is measured.Can use the quality of the reactive organosilan of routine techniques monitoring consumption.

Representational particle agitator 320 illustrates in greater detail in Fig. 3 B.Particle agitator 320 is the hollow circular cylinders with rectangular aperture 328.Agitator 320 be furnished with its axial alignment the axle 326, four rectangle lodicule 322 usefulness bolts be connected on this axle, this just is formed for the rabbling mechanism or the paddle wheel of particle in agitator 320.Blade 322 each self-contained two hole 44, to promote the circulation between the particle volume, this particle volume is included in each in four quadrants that formed by blade 322 and agitator cylinder 320.Describe to some extent in the occupation mode instance below of this device 300.

Fig. 4 A to Fig. 4 D schematically shows the different embodiment of second method of preparation treated porous granule disclosed herein, wherein is exposed to the time that steam carries out different length.Particle 420 can use the conventional drying technology dry before being exposed to steam.The particle 401 of embodiment shown in Fig. 4 A to Fig. 4 D has owing to being exposed to not commensurability surface absorption water and the not commensurability surface hydroxyl that the time of different length obtains in the steam.Fig. 4 D shows the longest steam open-assembly time, and Fig. 4 A shows the shortest open-assembly time, and Fig. 4 B and Fig. 4 C show intermediate quantity open-assembly time.Particle 440 in the embodiment shown in Fig. 4 A to Fig. 4 D is to obtain by being exposed to reactive organic silane compound, exists the zone of surface water and/or surface silicon alkanol to react in this chemical compound and the particle 401.With treated porous granule 405 dryings shown in Fig. 4 A to Fig. 4 D, absorb water to remove remaining surface.According to the duration that is exposed to steam (obtaining particle 401), treated porous granule 405 can have different level of coverage.Can cause uneven processing although be exposed to the short time steam, the exposure of long period can obtain more uniformly that hydrophobic group covers, and particle better, more consistent desiccant performance (as when being exposed to aqueous water).In certain embodiments, porous granule is exposed to about 1,2 or 3 hour of steam at least 15,20,25 or 30 minutes as many as.The time that is exposed to reactive organic silane compound also can influence the amount that hydrophobic group is gone up on the surface.

In certain embodiments, preparation is included in the organosilan that the organosilan steam arrives pre-reaction before the porous granule or prepolymerization vapor phase according to the method for treated porous granule of the present invention.This method is called " third party's method " hereinafter.Organosilan through the prepolymerization vapor phase forms dimer, trimer and higher oligomers, and the molecular size that the dimer of gained, trimer and higher oligomers will reach is enough to get rid of prepolymerized organosilan and infiltrates the probability in the hole of porous granule.For example, for the porous granule with extensive particle size distribution, this method possibly be favourable.Yet; Because the dimer of DDMS, trimer and the higher oligomers vapour pressure under environmental condition is lower; And tend on the inner surface of vacuum chamber, condense, so have necessary processing time or the optimization of treatment conditions (like temperature, pressure, organosilan and water, methanol or alcoholic acid vapour pressure or the like) otherwise of significantly increasing.

At some embodiment of third party's method of the outer surface that is used for handling porous granule 5, can advantageously use organosilan delivery of vapor to vacuum chamber and remain alternative method on surface of surface-treated particle.The sketch map of a kind of exemplary means 301 that is used for carrying out third party's method is schematically illustrated at Fig. 3 C.Shown in Fig. 3 C, can use two liquid keeper assemblies 360 (is used for reactive organic silane compound, and is used for water, methanol or ethanol) with delivery of vapor to vacuum chamber 340.Vacuum chamber 340 is connected to and can vacuum chamber 340 be evacuated to about 10 ^-6Holder (10 ^-4Pa) or the vacuum pump 350 of lower background pressure.The inside of vacuum chamber 340 is particle agitator 320 with single ingress port 382 (can as illustrating prevailingly among Fig. 3 B), first and second steam flows that this single ingress port 382 is used to make up.

Shown in Fig. 3 C, the compatible pipe 364 of vacuum that liquid keeper assembly can comprise sealing at one end, and the connection valve 366 that is used to open or close first vapor source that comprises reactive organic silane compound.Second vapor source can form in the following manner: make noble gas (like nitrogen) from source 376 through flow measurement device (like mass flow controller 374 and/or needle valve 372), get into gas diffusion tube 370 (said gas diffusion tube 370 immerses and is equipped with in aqueous water, methanol or the alcoholic acid gas bubbler 368) then, thus the equilibrated noble gas bubble 378 of formation and water, methanol or ethanol steam.

The noble gas that comprises water, methanol or ethanol steam is through annular mixing nozzle 380; Said herein noble gas mixes with organic silane compound; Get in the particle agitator 320 through outlet 382 then, said outlet 382 is connected to the inlet tube 330 (referring to Fig. 3 B) of particle agitator 320.Connect valve 366 and can be used to open or close first vapor source and second vapor source.Can use the quality of the reactive organosilan of conventional mass balance technical monitoring consumption.

In third party's method of handling porous granule, technological parameter is similar to those parameters of using in second method; Yet third party's method is intended to the premixed mixture of organosilan and water, methanol or ethanol steam is delivered to vacuum chamber.Through letting the nitrogen of known flow rate pass through water/methanol bubbler 368; In the generation of annular mixing nozzle 380 places true in advance quantitative steam, methanol vapor or ethanol steam or methanol vapor at least one, rapid polymerization organosilan monomer is fine with the oligomer that forms higher molecular weight.The amount of water, methanol or ethanol steam through being controlled at annular mixing nozzle 380 places can be accomplished the formation of required dimer, trimer or higher oligomers before product be deposited on the porous granule.

In some embodiment of second method of preparation treated porous granule disclosed herein or third party's method; Said method also comprises porous granule is exposed to the 3rd steam that comprises not with the volatile compound of reactive organosilan reaction; Again said porous granule is exposed in steam, methanol vapor or ethanol steam and the organosilan steam at least one; Wherein at least a portion of volatile compound is condensed at least a portion in said a plurality of holes of porous granule, thus closed interior hole surface at least in part.

In in these embodiment some, volatile compound is selected from molecular state nitrogen, carbon dioxide, methane, ethane and their combination.In some this type of exemplary embodiment; Said method also is included in porous granule is exposed to after second steam that comprises reactive organic silane compound; Basically in the hole, remove agglomerative volatile compound; Can be randomly, the step of wherein removing agglomerative VOC basically in the hole is through adding hot particle, particle being exposed to vacuum or their combination realizes.

At some embodiment, comprise that the vapour pressure of reactive organic silane compound under 25 ℃ all is 133Pa to 26,600Pa among above-mentioned any embodiment of second method as stated or third party's method.In certain embodiments, the step of handling the outer surface of porous granule is 1 at bulk vapour pressure, and 330Pa to 26 carries out under the condition of 600Pa.

At some embodiment, comprise among above-mentioned any embodiment of second method as stated or third party's method; Said a plurality of hole shows that all the mean pore sizes that has is maximum 4nm; And the step that porous granule is exposed to the steam that comprises reactive organic silane compound is 1 at bulk vapour pressure; 330Pa to 19 carries out under the condition of 950Pa.In other embodiments, said a plurality of holes show the mean pore sizes that has for greater than 4nm, and the step that porous granule is exposed to the steam that comprises reactive organic silane compound is 6 at bulk vapour pressure, and 650Pa to 26 carries out under the condition of 600Pa.For example, when second method of use was handled the porous granule with extensive pore-size distribution, a back vapour pressure scope was available.

At some embodiment, comprise among above-mentioned any embodiment of second method as stated or third party's method; Said method all also is included in porous granule is exposed to after second steam that comprises reactive organic silane compound; Basically in the hole, remove agglomerative steam, methanol vapor or ethanol steam; Can be randomly, the step of wherein removing agglomerative steam, methanol vapor or ethanol steam basically in the hole is through adding hot particle, particle being exposed to vacuum or their combination realizes.

At some embodiment, comprise among above-mentioned any embodiment of methods described herein that said method all also comprises treated porous granule is exposed to acetic acid.The particle of gained can comprise acetic acid in its hole, this particle can use with (for example) the treated porous granule as odor control agent.

At some embodiment, comprise that reactive organic silane compound is all by formula R among above-mentioned any embodiment of second method as stated or third party's method _xSiY _4-xExpression; Wherein each Y is hydrolyzable groups independently; This group can be selected from halogen (promptly-F ,-Cl ,-Br or I), alkoxyl (as having 1 to 6,1 to 4 or 1 to 2 carbon atoms), aryloxy group (like phenoxy group) or acyloxy (as having 1 to 6,1 to 4 or 1 to 2 carbon atoms); Each R is alkyl, thiazolinyl, aryl, aryl alkylene or alkyl arylene independently; In them each all can randomly be replaced by (like cyanic acid or halogen), and x is 1,2 or 3.In certain embodiments, x is 1 or 2.In certain embodiments, Y is halogen or alkoxyl.Usually, Y is a chlorine.In certain embodiments; Each R is that alkyl is (like methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, neopentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, 2; 2,4-tri-methyl-amyl, n-nonyl, positive decyl, dodecyl, AI3-06523 base, cyclopenta, cyclohexyl, suberyl or methylcyclohexyl).In certain embodiments, each R is methyl, ethyl or phenyl independently.In certain embodiments, each R is a methyl.Exemplary alkenyl groups comprises vinyl, pi-allyl and 5-hexene-1-base.Exemplary aryl comprises phenyl, naphthyl, anthryl and phenanthryl.The exemplary alkyl arlydene comprises o-tolyl, a tolyl, p-methylphenyl, xylyl and ethylphenyl, and exemplary aryl alkylene comprises benzyl and α-and β-phenethyl.Exemplary fluoro-alkyl comprises 3,3,3-trifluoro n-pro-pyl, 2,2,2,2', 2', 2'-hexafluoro isopropyl, 8-seven fluorine isopropyls.With formula R _xSiY _4-xThe multiple reactive organic silane compound of expression can (as from Huls America, Inc. (Cincinnati, OH) and Sigma-Aldrich) be purchased acquisition; With formula R _xSiY _4-xOther organic silane compounds of expression can be according to known method preparation.In certain embodiments, reactive organic silane compound is selected from dichlorodimethylsilane, dichloro-diethyl silane, trichloromethyl silane, chloro trimethyl silane and their combination.

Although have no intention to accept the constraint of opinion, it is believed that with chemical formula R _xSiY _4-xThe reactive organic silane compound of expression will be at first and the surface water hydrolytic reactions of pre-absorption, to form silanol.Silanol can with other molecule generation condensation reactions of surface-SiOH group and/or reactive organic silane compound, to generate short polysiloxane unit.Polysiloxanes with end-SiOH group also can react through condensation reaction and surface silanol groups.On the siloxanes of gained and the polysiloxanes by formula R _xSiY _4-xThe R base of the organic silane compound of expression makes that the surface of treated porous granule is hydrophobic.

Absorbent article

Treated porous granule according to the present invention can be used as (for example) and is incorporated into the desiccant in the absorbent article.Absorbent article has absorbent components and usually according to the wearing of absorbent article or occupation mode and distinctive other structural constituents.Exemplary absorbent articles sanitary towel 500 is shown in Fig. 5, but also can imagine other absorbent articles (using underwear like oxter liner, breast pad, antiperspirant pad, shoe pad, wound dressing, diaper, mattress or liner or incontinence).In certain embodiments, absorbent article is disposable.

Absorbent components according to the present invention comprises absorbing material and a plurality of treated porous granule as herein described.Absorbing material normally can absorb and keep the natural organic polymer of natural, the synthetic or modification of liquid (as liquid, aqueous).In certain embodiments, polymer is crosslinked.Term " crosslinked " is meant and makes common water-soluble material become water insoluble basically effectively but have any way of the material of swellability.The example of this type of mode comprises physical entanglement, domain, covalent bonding, ion complexation and association, hydrophilic association for example hydrogen bond and hydrophobic association or Fan Dewaerli.This type of absorbing material is intended to absorb rapidly liquid and usually with its maintenance, and can not discharge usually.At this used term " absorbing material " and do not mean that desiccant particles is included.In certain embodiments, the liquid that absorbing material can keep usually is at least about 0.05 gram/square centimeter, and this value can record through following method: absorbing material is immersed in the distilled water, sample is removed from water, sample was dripped 30 seconds.In certain embodiments, absorbing material absorbable liquid in water is at least about 100% (as at least 150%, 200%, 250%, 300%, 350% or 400%) of its weight, as confirming through the method for testing that provides in the following instance part.

Absorbent components can have any person in a plurality of shapes (like rectangle, I shape or T shape).The size of absorbent components and absorptive capacity should be consistent with expection wearer's size and the liquid load amount of being given by the desired use of absorbent article.Can and select it to form with the absorbing material subregion, so that liquid is moved to farther storage location from the initial position that pours in.This type of design can more effectively utilize the space in the absorbent article.In certain embodiments, absorbing material directly contacts with said a plurality of treated porous granules.For example, treated porous granule can mix with the SAP or the wood pulp that will be written in the absorbent article.In other embodiments, treated porous granule can be fixed on and will place the online of absorbent article.

In absorbent components according to the present invention and/or some embodiment according to a plurality of particles that comprise absorbing material of the present invention, absorbing material is cellulosic material, SAP or their mixture.In some embodiment according to absorbent components of the present invention; Absorbing material is that the acrylic acid series foam absorber is (like United States Patent(USP) No. 5; 817; The foam of describing in 704 (people such as Shiveley) and the list of references quoted thereof, said foam prepares through the polyreaction of for example high internal phase ratio emulsions).In certain embodiments, absorbent components comprises hydrophilic fibers (like wood pulp fluff, synthetic meltblown fibers or their combination) substrate and SAP particle.The SAP particle can mix or can mix unevenly with hydrophilic fibers with hydrophilic fibers basically equably.Equally, absorbing material and treated porous granule according to the present invention can be mixed uniformly basically or inhomogeneous blended.Hydrophilic fibers and ultra absorbing particle can place the desired zone of absorbent components selectively, to hold better and absorbing bodily secretions.The concentration of SAP particle also can change in the whole thickness of absorbent components.In certain embodiments, absorbent components comprises the lamination thing of fleece and SAP or superabsorbent material is remained on other appropriate device in the regional area.

In absorbent components according to the present invention and/or some embodiment according to a plurality of particles that comprise absorbing material of the present invention, the treated porous granule and the weight ratio of absorbing material are in the scope of 0.5:1 to 1:1.5.In certain embodiments, the amount of treated porous granule and absorbing material (as in the scope of 0.9:1 to 1:1.1) about equally.Yet for some application, the ratio of component of absorbent components can be outside this scope.

In some embodiment (like the embodiment of absorbent components disclosed herein or a plurality of particles), absorbing material is a wood pulp.In in these embodiment some, said absorbent components or a plurality of particle do not contain SAP basically.In these embodiment, usually, because the relative humidity of observed tester (no desiccant) is higher, so the beneficial effect that the humidity that treated porous granule according to the present invention provides reduces is more remarkable.Because the flowing fluid ratio SAP that wood pulp absorbs is few and the speed of absorption liquid is fast not as SAP, so the baseline values of humidity improves.

In some embodiment of a plurality of particles disclosed herein, absorbing particle or fiber comprise SAP.Comprise that treated porous granule disclosed herein and a plurality of particles of SAP can be used for absorbent article or the absorbent components that (for example) comprises other absorbing materials (like wood pulp).The ratio of SAP and treated porous granule can be in the scope of (for example) 99:1 to 1:99,95:5 to 5:95,90:10 to 10:90,85:15 to 15:85,80:20 to 20:80,75:25 to 25:75 or 70:30 to 30:70.

The SAP examples of material comprise gather (acrylic acid) and gather (methacrylic acid), gather (acrylamide), gather (vinyl ethers), maleic anhydride and vinyl ethers and alpha-olefin copolymer, gather (vinyl pyrrolidone), gather (vinyl morpholone), gather the alkali metal salt and the ammonium salt of (vinyl alcohol) and their mixture and copolymer.The other polymer that is applicable to absorbent components comprises the natural polymer of natural polymer and modification, the for example acryionitrile grafted starch of hydrolysis, acrylic acid grafted starch, methylcellulose, carboxymethyl cellulose, hydroxypropyl cellulose and natural gum (like alginate, yellow polysaccharide glue and locust bean gum).Also can use the natural absorbing polymeric and the mixture of synthetic absorbing polymeric wholly or in part.The SAP material is that those skilled in the art knows; And can be purchased acquisition widely (as deriving from Dow Chemical (Midland with trade name " DRYTECH 2035 "; Mich.) or with trade name " FAVOR SXM 880 " derive from Stockhausen Corporation (Greensboro, N.C.)).

Absorbing material (like SAP) can be any person in the multiple geometry.In certain embodiments, absorbing material is the form of discrete particle.Yet absorbing material also can be at least one the form in fiber, thin slice, rod, spheroid or the spicule.As general rule, according to the gross weight of absorbing body, the amount that high-absorbent material exists in absorbing body 36 is that about 5 weight % are to about 90 weight %.

In certain embodiments, absorbent article according to the present invention comprises disclosed absorbent components or a plurality of treated porous granule among the egative film of liquid permeable topsheet, liquid non-permeate and the above-mentioned any embodiment between top flat and egative film.This type of absorbent article generally includes sanitary towel, diaper and other Inconvenient articles.According to the decomposing schematic representation of the exemplary embodiment of absorbent article of the present invention shown in Fig. 5.

Referring to Fig. 5, along the thickness direction of absorbent article 500, top flat 520 is the layers that lean against on the user skin, is the ground floor of other exudates of contact liq or user therefore.Top flat 520 also plays the effect that the liquid that keeps in the skin of user and the absorbent components 560 is kept apart, and normally fits shape, softness and nonirritating.

Can use various materials to form according to the top flat in the absorbent article of the present invention, said material comprises apertured plastic films, Woven fabric, non-woven webs, porous foam and reticulated foams.In certain embodiments, top flat is a non-woven material.Exemplary non-woven material comprises the spunbond or meltblown fiber web of fibre-forming polymer long filament (like polyolefin, polyester or polyamide filaments), and the bonding carded web of natural polymer (like artificial silk or cotton fiber) and/or synthetic polymer (like polypropylene or polyester fiber).Nonwoven web can use surfactant (as, consumption is between about 0.05 weight % and the 0.5 weight %) carry out surface treatment or otherwise handle, with wettability and the hydrophilic of giving desired level.If used surfactant, then it can be that the internal additives of moving to the surface maybe can be applied to net through any conventional method (like spraying, printing, dipping or brushing).

Egative film 540 is sometimes referred to as the outer side covers part, and is apart from user layer farthest.Egative film 540 is formed by thermoplastic film (like polyethylene film) usually, and liquid is this thin film of impermeable basically.Egative film 540 is used for preventing to be contained in the body exudates moistening in the absorbent components 560 or pollutes the other materials of wearer's clothes, bedding or touching diaper.In certain embodiments, egative film is that original depth is the polyethylene film of about 0.5 mil (0.012 millimeter) to about 5.0 mils (0.12 millimeter).Polymeric film can be impression and/or through mute optical processing, thereby obtain outward appearance more attractive in appearance.In certain embodiments, egative film 540 comprises to be weaved or non-woven webs, and this net is configured or handles, to give the liquid impenetrability of desired level.In other embodiments, egative film 540 comprises by weaving or supatex fabric and the film formed lamination thing of thermoplasticity.In certain embodiments, egative film 540 comprises micropore " ventilative " material of steam or gas permeable, and liquid is this material of impermeable basically.For example, when egative film 540 comprised supatex fabric, egative film also can play the effect of the mating component that is used for machanical fastener.

In certain embodiments, also comprise acquisition layer 580 according to absorbent article of the present invention, as shown in Figure 5.Acquisition layer is provided, pours in thing with rapid acceptance, and absorb, keep, guiding or otherwise manage liquid, make liquid that can not leak into the goods outside.Acquisition layer also can be described as (for example) and pours in layer, blot coat, transfer layer or transport layer.For (for example) baby, acquisition layer can be handled usually pours in thing and is between about 60 and 100 milliliters (mL), pours in volume flow rate to be about 5 to 20 milliliters/second.

Acquisition layer 580 places between top flat 520 and another layer (like absorbent components 560) usually.Acquisition layer 580 usually top flat 520 with user skin facing surfaces below.Shift in order to improve liquid, with the upper surface of acquisition layer 580 and/or lower surface is attached to top flat respectively and absorbent components 560 possibly be favourable.Suitable conventional attachment techniques comprises at least one in binding agent bonding (as making use, solvent-borne type or heat-activated binder), hot adhesion, ultrasonic bonding, acupuncture or the puncture pore-forming.If (for example) acquisition layer 580 is bonded to top flat 520 with adhesive method, then the binding agent additional amount should be enough, thereby obtain required bond level, simultaneously not excessively confined liquid flow to the flow velocity the acquisition layer 580 from top flat 520.Various weaving with non-woven webs and foam can be used for constructing acquisition layer 580.For example, acquisition layer 580 can be melting and spraying or non-woven fabric layer that spunbond net constitutes by polyolefin filaments.This type of non-woven fabric layer can comprise conjugate fiber, biconstitutent fibre and the homopolymer fibre of short fiber or other length fiber, and the mixture of this fibrid and other types fiber.Acquisition layer 580 also can be by bonding carded web or air-laid webs natural and/or that synthetic fibers constitute.Bonding carded web can be the bonding carded web of (for example) powder, infrared bonding carded web or the bonding carded web of ventilating.The other example that pours in layer material is found in United States Patent(USP) No. 5,490,846 (people such as Ellis) and United States Patent(USP) No.s 5,364,382 (Latimer).Acquisition layer 580 can be made up of hydrophobic basically material, and this hydrophobic material can be randomly with surfactant treatment or otherwise processing, with wettability and the hydrophilic of giving desired level.In certain embodiments, acquisition layer 580 can have the homogeneous thickness of being generally and cross-sectional area.

According to some embodiment of absorbent article of the present invention, comprise among Fig. 5 in the illustrated embodiment, use hydrophilic basically tissue sheets 590 to help to keep the integrity of the air lay fibre structure of absorbent components 560.Can use one or more tissue sheets 590, or a tissue sheets 590 can be around the both sides of absorbent components.Tissue sheets 590 is arranged at least two of this absorbent components 560 around the absorbent components 560 usually mainly towards the surface, and is made up of absorbent cellulosic material (like crape oakum or high wet strength face-cloth).In certain embodiments, tissue sheets 590 can be constructed to provide the wicking layer, and said wicking layer helps to make liquid to be distributed in the absorbing material top in the absorbent components 560 rapidly.In these embodiment, tissue sheets 590 can be regarded as distribution layer, and it can move to the position (like absorbent components 560) that needs storage with fluid from the embryo deposit point.

Other types and/or extra distribution layer may reside in the absorbent article.These distribution layers can process by (for example) Woven fabric and nonwoven web (as, use the above-mentioned material that is used for top flat 520 and acquisition layer 580).

In some embodiment according to absorbent article of the present invention, said a plurality of treated porous granules 505 between top flat and absorbing material (as, be arranged in absorbent components).In these embodiment some, comprise in the illustrated embodiment of Fig. 5, said a plurality of treated porous granule 505 direct absorbing contacting materials (as, be arranged in absorbent components 560).In in these embodiment other, said a plurality of treated particles 505 can be arranged on (for example) acquisition layer 580 or between acquisition layer 580 and the face-cloth ply of paper 590.In certain embodiments, said a plurality of treated particles 505 can be arranged on (for example) absorbent components 560 belows, and they are still effective near the relative humidity the reduction user skin at this place.In certain embodiments; Absorbent article has elongated shape, longitudinal midline, transversal centerline and in the center of longitudinal midline and transversal centerline intersection; Wherein said a plurality of particle is in the centering district, but places at least one the either side of longitudinal midline or transversal centerline.In certain embodiments, absorbent article has elongated shape, longitudinal midline, transversal centerline and in the center of longitudinal midline and transversal centerline intersection, wherein said a plurality of particles are dispersed in the center." dispersion " meant between (for example) particle and is had the space.

In absorbent article according to the present invention, absorbent components and/or comprise among some embodiment of a plurality of particles of absorbing material; When at least a portion of said a plurality of particles is exposed to when liquid, aqueous; Compare with a plurality of contrast particles that do not comprise hydrophobic group; Said a plurality of particle can to a greater extent (as, with degree big by 5% at least, 10%, 15%, 20%, 25%, 30%, 40% or 50%) reduce relative humidity.A plurality of contrast particles that do not comprise hydrophobic group are meant identical with said a plurality of treated particles but without a plurality of particles of hydrophobic treatment.For example, before these type of a plurality of contrast particles were processed, its size was identical with said a plurality of treated particles with pore-size distribution, and chemical composition is identical with treated porous granule.The method of testing that is used for Humidity Measuring with shown in Fig. 2 A and Fig. 2 B that relative humidity in the absorbent article of contiguous user skin can partly be described according to (for example) following instance is measured.

Though undressed desiccant particles can be used for reducing the relative humidity in the absorbent article of contiguous user skin, undressed desiccant particles pours in absorption the liquid of absorbent article usually.Therefore the outer surface of desiccant and inner bore surface can not be used to be absorbed near the steam of absorbent article.By contrast, the outer surface of treated porous granule disclosed herein repels liquid, aqueous usually.The liquid that they absorb is many unlike undressed particle that kind, and therefore having more inner surface area is used to absorb steam.

In some embodiment according to absorbent article of the present invention, said a plurality of treated particles turn to the aqueous liquid stream of introducing the absorbent article top flat.Like this, said a plurality of treated particles are as distributed material (as stated), and it moves to the position that needs storage with fluid from the embryo deposit point.Treated particle makes the degree of fluid diversion can depend on the hydrophobicity on (for example) outer surface, and this hydrophobicity is relevant with contact angle usually.Therefore, can select treated porous granule is carried out hydrophobic treatment, so that the required amount of the fluid diversion of given absorbent article.In certain embodiments, said a plurality of treated porous granule is in the scope of 90 to 100 degree, 95 to 110 degree or 100 to 115 degree to the contact angle of water.

The required amount of fluid diversion that can be used for making given absorbent article according to the mixture of treated porous granule of the present invention and undressed porous granule.Flow divert that this type of mixture (for example) not only capable of using is provided by treated porous granule and enhanced humidity reduce both, but also the absorption to liquid that is provided by undressed porous granule capable of using.In certain embodiments, the treated porous granule and the weight ratio of undressed porous granule are in the scope of 0.5:1 to 1:1.5.In certain embodiments, the amount of treated porous granule and undressed porous granule (as in the scope of 0.9:1 to 1:1.1) about equally.Yet, for some application, can use the ratio outside this scope.In certain embodiments, treated porous granule and undressed porous granule are silica gel particle.

In certain embodiments, when treated porous granule is dispersed in when mixing in the zone of absorbent components or with absorbing material, said treated porous granule can be used for liquid stream is directed in the absorbing material.Usually expectation is, has enough spaces between the treated porous granule, to allow liquid to center on treated particle flow and to flow in the absorbing material.Spacing depends on the granularity of (for example) particle.

Desiccant particles can absorb moisture between the storage life.Treated porous granule according to the present invention can be kept in the pouch of moisture impermeable, to be used for storage and transportation.Have been found that treated porous granule is in that to be used for the standard pack of absorbent article (as be packaged in the Obstruct membrane or have the organosilicon liner and three folding structures) rate of water absorption stable.

Embodiments of the invention

In first embodiment, the present invention provides the treated porous granule that comprises outer surface and inner bore surface, and the major part at least of the outer surface of wherein treated porous granule comprises hydrophobic group, and wherein inner bore surface is undressed basically.

In a second embodiment, the present invention provides the described treated porous granule according to first embodiment, and wherein hydrophobic group comprises at least one in the alkyl or aryl, and wherein alkyl and aryl are randomly replaced by fluorine separately.

In the 3rd embodiment; The present invention provides the treated porous granule that comprises outer surface and inner bore surface; At least a portion of the outer surface of wherein treated porous granule comprises hydrophobic group; Said hydrophobic group comprises at least one in the alkyl or aryl, and wherein said alkyl and aryl are replaced by fluorine, and wherein inner bore surface for part is hydrophilic at least.

In the 4th embodiment; The present invention provides according to first, second or the described treated porous granule of the 3rd arbitrary embodiment, and wherein treated porous granule is treated silica gel particle, treated montmorillonitic clay particle, treated zeolite particles, treated molecular sieve or treated activated carbon particles.In in these embodiment some, treated porous granule is treated silica gel particle or treated activated carbon particles.

In the 5th embodiment, the present invention provides the described treated porous granule according to first to fourth arbitrary embodiment, wherein hydrophobic group comprise have alkyl, the siloxanes of aryl or their combination.

In the 6th embodiment; The present invention provides the described treated porous granule according to first to the 5th arbitrary embodiment; Wherein treated porous granule is the silica gel particle with outer surface; As confirming through the x-ray photoelectron power spectrum, the as many as 50 angstroms depth places of this silica gel particle outer surface have the silicon atom of maximum 5 atom %.

In the 7th embodiment, the present invention provides a plurality of particles that comprise according to the described treated porous granule of first to the 6th arbitrary embodiment.

In the 8th embodiment; The present invention provides the said a plurality of particles according to the 7th embodiment; Wherein be sprayed onto on the water surface when forming monolayer when said a plurality of particles; Said a plurality of particles of at least 75% float on the surface, and wherein said a plurality of particle absorbs the steam of its weight at least 20% after under 30 ℃ and 50% relative humidity, keeping 24 hours.

In the 9th embodiment; The present invention provides the said a plurality of particles according to the 7th or the 8th embodiment; Wherein under 30 ℃ and 80% relative humidity, the steam absorbance of said a plurality of particles is at least 60% of the steam absorbance of a plurality of contrast particles of not comprising said hydrophobic group.

In the tenth embodiment; The present invention provides described a plurality of particles according to the 7th to the 9th arbitrary embodiment; Wherein be exposed to when liquid, aqueous when at least a portion of said a plurality of particles; Compare with a plurality of contrast particles that do not comprise hydrophobic group, said a plurality of particles can reduce relative humidity to a greater degree.

In the 11 embodiment, the present invention provides described a plurality of particles according to the 7th to the tenth arbitrary embodiment, and wherein said a plurality of particles do not contain the particle that its outer surface and inner bore surface are all handled with hydrophobic group basically.

In the 12 embodiment, the present invention provides described a plurality of particles according to the 7th to the 11 arbitrary embodiment, and said a plurality of particles also comprise undressed desiccant particles.

In the 13 embodiment, the present invention provides described a plurality of particles according to the 7th to the 12 arbitrary embodiment, and said a plurality of particles also comprise color indicator.

In the 14 embodiment; The present invention provides described a plurality of particles according to the 7th to the 13 arbitrary embodiment; Said a plurality of particle also comprises absorbing particle or fiber, and said absorbing particle or fiber comprise at least one in super-absorbent polymer, hydrophilic nonwoven cloth or the wood pulp.

In the 15 embodiment; The present invention provides preparation according to the described treated porous granule of first to the 6th arbitrary embodiment or according to the method for the described a plurality of particles of the 7th to the 11 arbitrary embodiment; This method is included in the inner bore surface that makes porous granule and keeps the undressed basically while, handles the outer surface of porous granule with water-repelling agent.

In the 16 embodiment, the present invention provides the method according to the 15 embodiment, wherein has only the outer surface of porous granule just to handle with water-repelling agent.

In the 17 embodiment; The present invention provides according to the 15 or the method for the 16 embodiment, and the step of wherein handling the outer surface of porous granule comprises: through the plasma-deposited layer that comprises silicon, hydrogen and carbon that at least a portion outer surface of porous granule, forms.

In the 18 embodiment; The present invention provides the method according to the 17 embodiment; The step that wherein forms the layer that comprises silicon, hydrogen and carbon comprises: ionization includes the gas of organic silicon compound, and said organo-silicon compound are selected from alkyl silane, alkoxy silane, alkylidene polysilane, alkyl polysilane, thiazolinyl silane, aryl-silane and their combination.

In the 19 embodiment, the present invention provides according to the 17 or the method for the 18 embodiment, and that said method also comprises is siliceous with the fluorochemical pack processing, at least a portion of the layer of hydrogen and carbon.

In the 20 embodiment, the present invention provides the method according to the 19 embodiment, and wherein fluorochemical is selected from perfluoropropane, carbon tetrafluoride, fluoroform, difluoromethane, pentafluoroethane, perfluoropropene and perfluorobuttene and their combination.

In the 21 embodiment; The present invention provides according to the 19 or the method for the 20 embodiment, and the step of at least a portion of the layer of wherein siliceous with the fluorochemical pack processing, hydrogen and carbon comprises: through the plasma-deposited layer that comprises fluorine and carbon that at least a portion of the layer that comprises silicon, hydro carbons and carbon, forms.

In the 22 embodiment, the present invention provides according to the 15 or the method for the 16 embodiment, and the step of wherein handling the outer surface of porous granule comprises:

Porous granule is exposed to steam; Subsequently

Porous granule is exposed to second steam that comprises reactive organic silane compound.

In the 23 embodiment, the present invention provides the method according to the 22 embodiment, and wherein reactive organic silane compound is selected from dichlorodimethylsilane, trichloromethyl silane, chloro trimethyl silane and their combination.

In the 24 embodiment, the present invention provides according to the 22 or the method for the 23 embodiment, and the temperature of steam that wherein comprises reactive organic silane compound is for the highest 30 ℃.

In the 25 embodiment, the present invention provides the method according to the 22 to the 24 arbitrary embodiment, and the pressure that wherein comprises the steam of reactive organic silane compound is 400Pa at least.

In the 26 embodiment, the present invention provide comprise absorbing material with according to the bonded absorbent components of the described a plurality of particles of the 7th to the 13 arbitrary embodiment.

In the 27 embodiment, the present invention provides the absorbent components according to the 26 embodiment, and wherein absorbing material is at least one in wood pulp, super-absorbent polymer or the acrylic acid series foam.

In the 28 embodiment, the present invention provides absorbent article, this absorbent article comprise the egative film of liquid permeable topsheet, liquid non-permeate and between top flat and egative film according to the 26 or the absorbent components of the 27 embodiment.

In the 29 embodiment, the present invention provides absorbent article, and this absorbent article comprises the egative film of liquid permeable topsheet, liquid non-permeate and the said a plurality of particles according to the 14 embodiment between top flat and egative film.

In the 30 embodiment, the present invention provides according to the 28 or the absorbent article of the 29 embodiment, and wherein said a plurality of particles are between top flat and absorbing material.

In hentriaconta-embodiment; The present invention provides the described absorbent article according to the 28 to the 30 arbitrary embodiment; Wherein absorbent article has elongated shape, longitudinal midline, transversal centerline and in the center of longitudinal midline and transversal centerline intersection; And wherein said a plurality of particle is in the centering district, but places at least one the either side of longitudinal midline or transversal centerline.

In the 32 embodiment; The present invention provides the described absorbent article according to the 28 to the 30 arbitrary embodiment; Wherein absorbent article has elongated shape, longitudinal midline, transversal centerline and in the center of longitudinal midline and transversal centerline intersection, and wherein said a plurality of particle is dispersed in the center.

In the 33 embodiment, the present invention provides the described absorbent article according to the 28 to the 32 arbitrary embodiment, and wherein said a plurality of particles turn to the aqueous liquid stream of introducing the absorbent article top flat.

In the 34 embodiment, the present invention provides the purposes of following particle as desiccant: according to the described treated porous granule of first to the 6th arbitrary embodiment; Or according to the described a plurality of particles of the 7th to the 14 arbitrary embodiment.

In the 35 embodiment, the present invention provides the purposes according to the described treated porous granule of the 34 embodiment, and wherein desiccant is exposed to liquid, aqueous.

In the 36 embodiment, the present invention provides the purposes of following particle as odor control agent: according to the described treated porous granule of first to the 6th arbitrary embodiment; Or according to the described a plurality of particles of the 7th to the 14 arbitrary embodiment.

In the 37 embodiment, the present invention provides the purposes according to the described treated porous granule of the 35 embodiment, and wherein odor control agent is exposed to liquid, aqueous.

Following limiting examples further illustrates embodiments of the invention, but concrete material of being mentioned in these instances and content thereof and other conditions and details all should not be interpreted as improper restriction of the present invention.

Instance

Method of testing

Floating test

(about 10mL) adds in the vial of 20mL with deionized water, uses spoon slicker that particle is sprayed on the water surface carefully then, and its sprinkling amount is the treated particle that is enough to form monolayer.For particle instance 1 to 18, illustrative examples 1 to 8 and comparative example 1, the amount of treated particle is about 1 gram.The particle that visual examination is treated, and estimate the percentage ratio of buoyant treated particle.When swimming on the water surface, think that then treated particle has passed through floating test at least about 75% treated particle.

When diameter particle size is that the undressed silica gel of 0.5mm to 1.0mm (can be available from AGMContainer Controls; Inc. (Tucson; AZ) A type silica gel, production code member: 920014) accept should test the time, particle sink to the bottle bottom and be attended by usually " crack " sound.

The surface analysis of treated particle

Use following steps that particle is carried out chemical analysis of the electron spectrum (ESCA).Use is carried out three time replicate analysis available from the x-ray photoelectron spectroscopy of Kratos Analytical (Chestnut Ridge, New York) to the surface of sample with trade name " AXIS ULTRA ", and this instrument uses monochromatic Al x-ray source exciting light electronics.At 90 ° of photoelectrons that fly away from the detection emission of place, angle with respect to sample surfaces.Through the main peak area being carried out integration and using appropriate sensitivity factor, confirm surface composition from the spectrum that obtains.ESCA is quantitative analysis; And the sampling depth of representative between

and

, this degree of depth depend on the electronic kinetic energy of the atomic core level electronics of launching in material and this material of research.

The steam absorbance

The steam of measuring treated particle, undressed particle, wood pulp (paper pulp) and super-absorbent polymer (SAP) absorbs.Weighing two gram samples place bottle, then bottle are placed glass jar, and sample is exposed under 30 ℃ and 50% the relative humidity.Bottle is shifted out wide mouthed bottle, add a cover, and weighing.In the change of following table point measurement instruction time weight, and record.

The aqueous water absorbance

Cellular glass material filter is assembled on the conical flask of band side arm.Side arm is connected to indoor vacuum system.Frit is used water-wet, and apply vacuum and make its drying.Particle (2 gram) is placed on the frit, inject the 10mL deionized water along glass wall then.Let water keep in touch particle 3 minutes.After 3 minutes, inhale vacuum through side arm, weighing enters the water in the flask.Calculate the water absorptance values then.The particle of each type is all repeated this step 3 time.

Particle instance 1 to 4

(2480 types are used for particle is carried out Cement Composite Treated by Plasma from PlasmaTherm (St.Petersburg Florida) is purchased acquisition) with business-like parallel plate capacitor manifold type active-ion-etch device.Be arranged under the situation near the ion sheath of electrode at sample and carry out Cement Composite Treated by Plasma.This reaction vessel comprises earthing chamber electrode and drive electrode.This chamber is cylindrical, and internal diameter is 762mm (30 inches), the high 150mm (6 inches) of being.Be provided with the circular electrode that a diameter is 686mm (27 inches) in chamber interior, and the 3kW radio-frequency power supply that is connected with matching network and under the 13.56MHz frequency, operates.Use the Roots blower that drives by mechanical pump to the chamber interior evacuation.Unless otherwise indicated, otherwise chamber in pressure of foundation be 0.67Pa (5 millitorr).Through mass flow controller or needle valve the process gas that gets into chamber is measured.Accomplish all Cement Composite Treated by Plasma through sample being placed the glass culture dish on the plasma reactor drive electrode.

The Cement Composite Treated by Plasma of silica gel divides two independent steps to accomplish.In first step, in tetramethylsilane (TMS) plasma, handle particle, be deposited on the outer surface of particle will have the silicone layer that connects methyl.In second step, use the perfluoropropane plasma to generate CF from the teeth outwards ₃, CF ₂With the CF group.

With silica gel particle (A type silica gel; It is reported that its average pore size is in about scope of 2 to 3nm; Can be available from AGM Container Controls; Inc., production code member: 920014) placing the degree of depth is about 0.125 to 0.25 inch glass culture dish, then glass culture dish is placed on the drive electrode of PlasmaTherm response system.Said chamber is evacuated to the pressure of 10 millitorrs (1.3Pa), and tetramethylsilane is introduced with the flow velocity of 150 standard cubic centimeters per minute (sccm), under 1000 watts power, produces plasma.Operation is at room temperature carried out, and operating pressure is 50 millitorrs (6.7Pa).The persistent period that plasma is opened during first step is 10 minutes, after this closes gas, emptying chamber, and the particle in the hand mix culture dish.To chamber evacuation, pressure is fallen back less than 10 millitorrs (1.3Pa) once more.Subsequently the tetramethylsilane steam is introduced with the flow velocity of 150sccm again, lighted plasma and under 1000 watts power, keep 10 fens clock times again.After this, emptying chamber once more, the hand mix desiccant particles with the chamber evacuation blood pressure lowering, is introduced the tetramethylsilane steam again, and plasma is kept last 10 minutes clock times.The total time of using the tetramethylsilane steam to carry out Cement Composite Treated by Plasma is 30 minutes.After the Cement Composite Treated by Plasma for the third time of carrying out with the tetramethylsilane steam finishes, with perfluoropropane (C ₃F ₈) gas introduces in the chamber with the flow velocity of 150sccm, rekindle plasma, and under 1000 watts, keep 10 minutes.Operating pressure is 50 millitorrs (6.7Pa).After this, close gas, and chamber is emptied to atmospheric environment.Repeat C again ₃F ₈Cement Composite Treated by Plasma twice, and at these twice C of 10 minutes ₃F ₈Particle between the plasma treatment step in the manual stir culture ware.Therefore, C ₃F ₈The total time of Cement Composite Treated by Plasma also is 30 minutes.

Instance 2 to 4 prepares according to the method for instance 1 separately, the different Cement Composite Treated by Plasma total times that is to use indication in the following table 1.For in the instance 2 to 4 each, identical is all to light plasma once more three times, but changes the time of keeping plasma, with the processing total time shown in obtaining showing.In the instance 1 to 4 each all is kept in the glass jar, to avoid before test, absorbing moisture.In the instance 1 to 4 each has all been passed through the floating test described in the above-mentioned Test Methods section, and the percentage ratio of floating granules provides in following table 1.

Table 1

Use is according to the ESCA evaluation example 1 to 4 of above-mentioned method of testing.The result is shown in the following table 2.

Table 2

Use above-mentioned method of testing evaluation example 1 to 3, undressed silica gel, SAP (can trade name " AQUA KEEP SA60S " available from the steam absorbance of Sumitomo Seika (Osaka, Japan)) and the wood pulp that from can the sanitary towel of trade name " BODYFIT ", takes out available from Unicharm Corp..The result is shown in the following table 3.

Table 3

The time that a measures SAP and wood pulp is 0,1.03,2.07,3.13,4.17,5.33,6.42,22.6 and 23.63 hour.

Particle instance 5 and 6

For instance 5 and 6, and silica gel particle (can be available from AGM Container Controls, Inc., production code member: 920014) use following method of plasma processing to handle, said method allows during Cement Composite Treated by Plasma, to mix.Chamber is constructed by rustless steel, and comprises horizontal mixing paddle, and this blade rotates with 6 rev/mins speed continuously.Chamber is connected to the Roots blower (Leybold, model WSU 150) that is driven through cyclone separator and particle filter by drying machinery pump (Edwards, model DP40).The rectangular electrode of 8.5 inches (21.6cm) * 15 inch (38.1cm) is positioned on the silica gel particle bed, and is connected to 40kHz generator (Advanced Energy, model PE5000) to generate plasma.The particle of about 1 cubic feet (5kg) is packed in the chamber, then chamber evacuation is depressurized to the pressure of foundation that is lower than 200 millitorrs (26.7Pa).Cement Composite Treated by Plasma is carried out in two steps, the wherein operating sequence of tetramethylsilane and perfluoropropane plasma such as instance 1, different is particle be blended in plasma treatment step during carry out continuously.At first, the tetramethylsilane steam is introduced in the chamber with the flow velocity of 300sccm, lighted plasma and under 500 watts power, kept 4 hours.After this, stop the tetramethylsilane steam flow, feed the perfluoropropane stream of 300sccm then.Light plasma once more, and under 500 watts power, kept again two hours with perfluoropropane gas.For tetramethylsilane and perfluoropropane, the pressure during the Cement Composite Treated by Plasma is about 500 to 1000 millitorrs (66.7 to 133Pa).In the instance 5 and 6 each has all been passed through the floating test described in the above-mentioned Test Methods section, and the visual estimator of floating granules is 90%.

The water absorbance of the wood pulp that uses above-mentioned method of testing evaluation example 1 to 3 and 5, undressed silica gel, SAP (can trade name " AQUA KEEP SA60S " available from Sumitomo Seika) and from can the sanitary towel of trade name " BODYFIT ", take out available from Unicharm Corp..The result is shown in the following table 4.

Table 4

Water absorbance (gram)

SAP	Wood pulp	Unprocessed	Instance	1	Instance 2	Instance 3	Instance 5
								9.97	9.80	1.10	0.37	0.60	0.70	0.62

Particle instance 7

Preparation instance 7 described in instance 5 and 6, different is introduces the tetramethylsilane steam in the chamber with the flow velocity of 360sccm, lights plasma and under 500 watts power, keeps 60 minutes.Do not introduce perfluoropropane gas.Instance 7 has passed through the floating test described in the above-mentioned Test Methods section, has 90% particle floating.

Illustrative examples 1 and particle instance 8 to 10

With the device shown in Fig. 3 A and Fig. 3 B 300 handle silica gel particles (can be available from AGMContainer Controls, Inc., production code member: 920014).Particle agitator 320 is the hollow circular cylinder (6cm length * 5.5cm horizontal diameter) of 200cc, locate to have rectangular aperture 328 at the top (4.5cm * 3.5cm).Agitator 320 is furnished with the axle 326 with its axis alignment.Axle has rectangular cross section, and (1cm * 1cm), four orthogonal blade 322 usefulness bolts are connected on this axle, and this just is formed for paddle wheel that particle is rolled.Each self-contained two hole 324 of blade, to promote the circulation between the particle volume, this particle volume is included in each in four quadrants that formed by blade and agitator cylinder.Select the size of blade, so that it is 4mm with side distance and tip spacing between the stirring wall.The particle agitator has gas access port 330 in the cylinder at.Particle agitator 320 placed be connected to mechanical pump 350 (in can the vacuum chamber 340 of trade name " WELCH 1374 oil-sealed rotary pumps " (WELCH 1374Mechanical Vacuum Pump) available from Welch Vacuum Technology (Niles, IL)).

With two liquid keeper assemblies 360 steam is delivered to vacuum chamber from fluid supply, an assembly is used for dichlorodimethylsilane (DDMS), and another assembly is used for deionization (DI) water.Each liquid keeper assembly all (can be available from MDC Vacuum Products (Hayward by the compatible glass tubing 362,364 of vacuum of sealing at one end; CA)) be used to control the open/close valve 366 that is connected of vapor source and (can constitute available from Swagelok company (Solon, OH)).

Place temperature to be made as the baking oven dried overnight (that is, more than 12 hours) of 155 ℉ (68 ℃) silica gel particle.100 grams are placed the particle agitator through the silica gel particle of oven drying, be depressurized to 500 millitorrs (66.7Pa) or littler with 350 pairs of chamber evacuations of pump.With being installed in the convectron manometry pressure on the chamber.Through closing chamber valves chamber and vacuum pump are broken off.Open the valve that is connected to the DI water source, to let steam get into the inside of chamber.After constant pressure reaches 4 to 5 holders (533-667Pa), valve-off.The particle stirrer shaft is with the speed rotation of about 2rpm.Silica gel particle was exposed to steam 20 minutes.Be exposed to steam after 20 minutes, chamber evacuation is being depressurized to 1 holder (133Pa) or littler, carrying out particle simultaneously and stir.Open the DDMS valve then.DDMS has 135 holders (1.8 * 10 under 25 ℃ ⁴Pa) vapour pressure is so fluid supply is without any need for external heat.After 30 seconds, constant pressure reaches 3 holders (400Pa), closes the DDMS valve.Through constant speed rotating spoon axle, make silica gel particle in chamber, be exposed to the not commensurability time of DDMS steam.After the required processing time, chamber is found time, and then be exposed to steam 2 minutes, to remove any remaining DDMS steam.After whipping process stops, again chamber being found time and be discharged into environmental condition.

For illustrative examples 1 and particle instance 8,9 and 10, the time that is exposed to the DDMS steam was respectively 5,10,15 and 20 minutes.In illustrative examples 1 and the particle instance 8 to 10 each is all descended dried overnight in 155 ℉ (68 ℃) in baking oven, and is kept in the glass jar, to avoid before evaluation, absorbing moisture.

Adopt the floating test evaluation illustrative examples 1 and particle instance 8 to 10 described in the above-mentioned Test Methods section.For illustrative examples 1, there is 40 to 50% treated particle floating.For particle instance 8 and 9, there is 70 to 80% treated particle floating, and for particle instance 10, there is 90% treated particle floating.

Use is estimated illustrative examples 1 and particle instance 8 to 10 according to the ESCA of method of testing mentioned above.The result is shown in the following table 5.

Table 5

Illustrative examples 2 and 3 and particle instance 11 and 12

Illustrative examples 2 and 3 and the conventional method preparation of instance 11 and 12 operation instructions example 1 and particle instance 8 to 10, but have following modification.The silica gel through oven drying of monolayer (40 gram) is placed the aluminum pallet, pallet is placed 30 ℃ of different times shown in the humidity cabinet maintenance following table 6 with 80% relative humidity, carry out 5 minutes DDMS steam treated then.In particle stirring and processing procedure, do not use steam.Humidity exposure time and silica gel have been shown in the following table 6 to be operated before and weight afterwards in humidity exposure.

Table 6

The particle instance	Illustrative examples 2	Illustrative examples 3	11	12
					The humidity exposure time before DDMS handles (minute)	5	10	15	30
Particle weight (gram) before the humidity exposure	40.7	38.6	41.5	42.0
					Particle weight (gram) after the humidity exposure	43.6	44.0	48.3	53.5
Moisture before DDMS handles increases (gram)	3.0	5.4	6.9	11.6
					Moisture before DDMS handles increases (%)	7.3	13.9	16.6	27.6

Illustrative examples 2 and 3 and particle instance 11 and 12 in each all in baking oven in the following dried overnight of 155 ℉ (68 ℃), and be kept in the glass jar, to avoid before evaluation, absorbing moisture.Adopt in the method for testing mentioned above floating test to illustrative examples 2 and 3 and particle instance 11 and 12 estimate.For illustrative examples 2, there is 30 to 40% treated particle floating.For illustrative examples 3, there is 50 to 60% treated particle floating.For particle instance 11, there is 80% treated particle floating, and for particle instance 12, there is 90% treated particle floating.

Illustrative examples 2 and 3, particle instance 11 and 12 and undressed silica gel estimate the steam absorbance with above-mentioned method of testing, different is carries out this evaluation under 30 ℃ and 80% relative humidity.The result is shown in the following table 7.

Table 7

Use above-mentioned method of testing to estimate illustrative examples 2 and 3, instance 11 and 12, undressed silica gel, SAP (can trade name " AQUA KEEP SA60S " available from Sumitomo Seika) and the water absorbance of the wood pulp that from can the sanitary towel of trade name " BODYFIT ", takes out available from Unicharm Corp..The result is shown in the following table 8.

Table 8

Water absorbance (gram)

SAP	Wood pulp	Unprocessed	Illustrative examples 2	Illustrative examples 3	Instance 11	Instance 12
							9.97	9.80	1.10	0.74	0.66	0.61	0.49

Illustrative examples 4 and particle instance 13 to 15

The conventional method preparation of illustrative examples 4 and particle instance 13 to 15 operation instructions example 1 and particle instance 8 to 10, but have following modification.The silica gel through oven drying of monolayer (50 gram) is placed the aluminum pallet, then with pallet be exposed to 30 ℃ with the different time shown in 80% the relative humidity maintenance following table 9, carry out 15 minutes DDMS steam treated again.In particle stirring and processing procedure, do not use steam.Humidity exposure time and silica gel have been shown in the following table 9 to be operated before and weight afterwards in humidity exposure.

Table 9

Instance	Illustrative examples 4	Instance 13	Instance 14	Instance 15
					The humidity exposure time before DDMS handles (minute)	5	10	15	30
Desiccant weight (gram) before the humidity exposure	49.4	50.2	49.9	49.7
					Desiccant weight (gram) after the humidity exposure	52.2	56.0	57.9	62.6
Moisture before DDMS handles increases (gram)	2.9	5.7	8.1	12.9
					Moisture before DDMS handles increases (%)	5.8	11.4	16.2	25.9

In illustrative examples 4 and the particle instance 13 to 15 each is all descended dried overnight in 155 ℉ (68 ℃) in baking oven, and is kept in the glass jar, to avoid before evaluation, absorbing moisture.

Adopt the floating test in the above-mentioned method of testing that illustrative examples 4 and particle instance 13 to 15 are estimated.For illustrative examples 4, there is 30 to 40% treated particle floating.For particle instance 13 and 15, there is 95% treated particle floating, and for particle instance 14, there is 90% treated particle floating.

Illustrative examples 4 and particle instance 13 to 15 and undressed silica gel is with above-mentioned method of testing evaluation steam absorbance, and different is carries out this evaluation under 30 ℃ and 80% relative humidity.The result is shown in the following table 10.

Table 10

Use above-mentioned method of testing to estimate illustrative examples 4 and particle instance 13 to 15, undressed silica gel, SAP (can trade name " AQUA KEEP SA60S " available from Sumitomo Seika) and the water absorbance of the wood pulp that from can the sanitary towel of trade name " BODYFIT ", takes out available from Unicharm Corp..The result is shown in the following table 11.

Table 11

Water absorbance (gram)

SAP	Wood pulp	Unprocessed	Illustrative examples 4	Instance 13	Instance 14	Instance 15
							9.97	9.80	1.10	0.93	0.61	0.64	0.60

Particle instance 16

Instance 16 is according to the method preparation of illustrative examples 1 and particle instance 8 to 10, and different is to have following modification.The silica gel particle that can directly use is exposed to following 1 hour of the relative humidity of 90 ℉ and 90%.Weight has increased by 4.9%.In the particle of humidity (100 gram) the particle agitator of packing into, and with vacuum chamber from ambient pressure 760 holders (1.0 * 10 ⁵Pa) pumped down to 10 holder (1.3 * 10 ³Pa).Reach 10 holders (1.3 * 10 at constant pressure ³Pa) after, slightly take out valve itself and vacuum pump are broken off through closing.Start the particle tumble process, open the DDMS cap relief valve to agitator then.After 5 minutes, close the DDMS valve.Slightly take out valve chamber was found time 2 minutes through opening, to remove HCl steam and any undressed silane steam.At last, discharged air in chamber, and take out treated sample.Instance 16 has passed through the floating test described in the above-mentioned Test Methods section, has 99% treated particle floating.

Illustrative examples 5

Illustrative examples 5 is according to the method preparation of illustrative examples 1 and particle instance 8 to 10, and different is to have following modification.With pack into the particle agitator of the inside that is arranged in vacuum chamber of about 100 gram silica gel that can directly use.Slightly take out valve at a slow speed chamber is carried out pumped down through opening.In case constant pressure reaches 10 holders (1.3 * 10 ³Pa), just slightly take out valve chamber is broken off through closing.Open agitator, and make the DDMS valve open, to be used for steam treated particle.After handling 5 minutes, chamber was found time 2 minutes and is disposed to environmental condition.Take out treated particle.When estimating according to above-mentioned floating method of testing, the treated particle of no illustrative examples 5 is floating.

Illustrative examples 6

Illustrative examples 6 is according to the method preparation of illustrative examples 5, and different is that chamber evacuation is depressurized to 100 holders (1.3 * 10 ⁴Pa), and DDMS handle in 100 holders (1.3 * 10 ⁴Pa) carried out under 5 minutes.When estimating, there is the treated particle of 3% illustrative examples 6 floating according to above-mentioned floating method of testing.

Illustrative examples 7

Illustrative examples 7 is according to the method preparation of illustrative examples 1 and particle instance 8 to 10, and different is to have following modification.The 100 gram silica gel that can directly use are packed in the particle agitator and placed vacuum chamber.Chamber evacuation is depressurized to 120 millitorrs (16Pa).At this moment, chamber is separated with vacuum-pumping system.Produce steam from liquid water source.Open the particle agitator, particulated bed is rolled.Make constant pressure rise to 2.50 holders (333Pa) through filling steam from 120 millitorrs (16Pa).Under this pressure, rolled 10 minutes by particle through being exposed to steam.After 10 minutes, let in the air admission chamber, make pressure rise to 10 holders (1.3 * 10 ³Pa).Reach 10 holders (1.3 * 10 at constant pressure ³Pa) after, close drain valve, and the DDMS cap relief valve is opened 5 minutes to handle particle.After 5 minutes,, and be disposed to environmental condition with chamber evacuation blood pressure lowering 2 minutes.When estimating, there is the treated particle of 50% illustrative examples 7 floating according to above-mentioned floating method of testing.

Illustrative examples 8

Illustrative examples 8 is according to the method preparation of illustrative examples 1 and particle instance 8 to 10, and different is to have following modification.The 100 gram silica gel that can directly use are packed in the particle agitator and placed vacuum chamber.Chamber evacuation is depressurized to 500 millitorrs (67Pa).The beginning particle stirs, and lets in the steam inlet chamber.With external heat chuck heating aqueous water bearing assembly, to improve to indoor speed of sending steam.When water seethed with excitement, constant pressure rose to 11 holders (1.5 * 10 immediately ³Pa).At this moment, open the DDMS valve, to handle to chamber.After 5 minutes, chamber was found time 2 minutes, and enter air.When estimating, there is the treated particle of 35% illustrative examples 7 floating according to above-mentioned floating method of testing.

Particle instance 17

Particle instance 17 is according to the method preparation of illustrative examples 8, and different is to have following modification.Let in the steam inlet chamber, reach 25 holders (3.3 * 10 up to constant pressure ³Pa).Make silica gel particle be exposed to steam after 15 minutes, chamber evacuation is depressurized to 10 holders (1.3 * 10 ³Pa), and 10 hold in the palm (1.3 * 10 ³Pa) DDMS that carried out under the pressure 5 minutes handles.After the processing, chamber was found time 2 minutes, and enter air.Instance 17 has passed through the floating test described in the above-mentioned Test Methods section, has 90% treated particle floating.

Estimate the steam absorbance of illustrative examples 5 to 8, particle instance 17 and undressed silica gel with above-mentioned method of testing, different is carries out this evaluation under 30 ℃ and 80% relative humidity.The result is shown in the following table 12.

Table 12

Estimate illustrative examples 5 to 8, particle instance 16 and 17 and the water absorbance of undressed silica gel with above-mentioned method of testing, but have following modification.Measure the weight enter the water in the flask, on the contrary, measured particle before be exposed to water with afterwards weight.Illustrated in the following table 13 particle before being exposed to water with the difference of afterwards weight.

Table 13

Water absorbance (gram)

Unprocessed	Illustrative examples 5	Illustrative examples 6	Illustrative examples 7	Illustrative examples 8	Instance 17	Instance 16
							0.81	0.74	0.77	0.74	0.73	0.71	0.69

Particle instance 18 and comparative example 1

Particle instance 18 and the method preparation of comparative example 1 according to illustrative examples 1 and particle instance 8-10, different is to have following modification.Be exposed to dampness (30 ℃ and 80% relative humidity) at the particle that carries out directly to use before the DDMS steam treated.During humidity exposure, the moisture of the part of per 10 to 20 minutes inspection particles increases, and reaches 13.0 weight % up to instance 18, and comparative example 1 reaches 5.9 weight %.With pack into the particle agitator of the inside that is arranged in vacuum chamber of about 1000 gram humidity exposure silica gel.This particle agitator particle agitator more used than particle instance 1 to 17 and illustrative examples 1 to 8 is big, and its cylinder length is 12 inches (30.5cm), and diameter is 7 inches (17.8cm).Rectangular aperture in the cylinder top is of a size of 11.25 inches * 6.5 inches (28.6cm * 16.5cm).Each blade 322 all is the rectangle with hole, and this rectangular dimension is 11.75 inches * 3.5 inches (29.8cm * 8.9cm).Chamber evacuation is depressurized to 10 holders (1.3 * 10 ³Pa).Open agitator then, stir, open the DDMS valve, to be used for 5 minutes steam treated to particle with the speed of 4 rev/mins (rpm).After 5 minutes steam treated, close the DDMS valve, let particle in chamber, react again 5 minutes with DDMS.Total coprocessing is after 10 minutes, and chamber was found time 2 minutes and is disposed to environmental condition.Take out treated particle and under 180 ℃, carry out 2 hours after drying, to remove the unreacted moisture that adsorbs in the particle.Particle instance 18 has all passed through the floating test described in the above-mentioned Test Methods section with comparative example 1, has greater than 95% treated particle floating.

Estimate the steam absorbance and the water absorbance of particle instance 18, comparative example 1 and undressed silica gel with above-mentioned method of testing.Carry out having following modification when the water absorbance is estimated: measure the weight that enters the water in the flask, on the contrary, measured particle before being exposed to water with afterwards weight.Carry out the water absorbance when estimating, for undressed silica gel, particle was 0.81g with afterwards weight difference before being exposed to water, and this difference is 0.70g for particle instance 18, and difference is 0.61g for comparative example 1.Carry out having following modification when the steam absorbance is estimated: under 30 ℃ and 80% relative humidity, carry out this evaluation.The result of steam absorbance has been shown in the following table 14.

Table 14

Use can trade name " TOF.SIMS.5 " (M ü nster, analyzes particle instance 18 (with particle instance 1 similar particle) and undressed silica gel through flight time secondary ion mass spectrometry (SIMS) (TOF-SIMS) instrument Germany) available from ION-TOF GmbH.Use to the 1 described method preparation and particle instance 1 similar particle of particle instance, different is, with TMS Cement Composite Treated by Plasma 60 minutes, with perfluoropropane Cement Composite Treated by Plasma 40 minutes.25keV Bi+ primary ions Shu Jinhang high-quality resolution rate negative ions with pulse is analyzed, and wherein beam diameter is about 3 microns (μ m), and analyzing area is 500 * 500 μ m.SIMS has monolayer sensitivity, and analysis depth is in 10 to 20 dusts

scope.

Through the particle of each instance or the particle of undressed silica gel all are placed to the outer surface of analyzing particle on the two-sided tape.They are rived preparation particle cross section through each particle is placed under the optical microscope and with clean razor blade.This step causes particle to split at random, and is enough to exposed inner.Cross section is placed on the two-sided tape, the inside face of exposure is upwards shelved, to be used for analysis.

The outer surface of undressed silica gel particle shows distinctive SIMS silicon dioxide ion: Si+, SiOH+, SiO ₂-, SiO ₂H-, SiO ₃-, SiO ₃H-, Si ₂O ₅H-, and other Si _xO _yH _z-type small ion.The Na, Fe, Ba, hydrocarbon, S and the Cl that also have trace on the surface.Observe few fluorine or silane or siloxanes ion.

Show to have many fluorocarbon ions with the outer surface of particle instance 1 similar particle, comprise CF+, CF ₂H+, CF ₃+, C ₃F ₃+, C ₂F ₅+, C ₃F ₅+, C ₃F ₇+, F-, F ₂-, F ₂H-, CF ₃-, CF ₃O-, C ₃F ₃-, C ₄F ₉-and other C _xF _y+ and C _xF _y-type small ion.Lip-deep silicon dioxide ion concentration is extremely low.

The peculiar silicon dioxide ion that the outer surface of particle instance 18 shows is with detected identical on undressed silica gel particle, but the other ion that characterizes silane treatment in addition: CH ₃Si+, (CH ₃) ₃Si+, CH ₃SiO-, CH ₃SiO ₂-and polydimethylsiloxane ion (117+, 133+, 147+, 207+, 221+, 281+, 325+, 149-, 223-).Chlorinity is about 3 times high on the undressed silica gel outer surface.

The peculiar silicon dioxide ion that both cross sections of the particle that is similar to particle instance 1 and particle instance 18 show has only seldom or does not have fluorine or silane with detected identical on undressed silica gel outer surface.Instance 5 inner only ions are the F-of m/z 19, compare with undressed silica gel particle, and this ion slightly increases.Not having on the inside can detected fluorocarbon ions.

For with the more treated particle of sxemiquantitative mode, the various ionic counting that can pay close attention to material with representing is compared with the ion of representing the silicon dioxide background and is asked ratio.For the particle that is similar to particle instance 1, selection ratio CF ₂+/29Si+, F-/SiO ₂-and F ₂-/SiO ₂-.The ion count results of cation shows, is reduced to about 1/1000th from the surface to inner F-signal.For particle instance 18, selection ratio CH ₃Si+/SiOH+, [CH ₃SiO-+CH ₃SiO ₂-]/[SiO ₂H-+SiO ₃-+SiO ₃H-] and Cl-/SiO ₂-.The ion count results demonstration of cation is reduced to about 1/200th from the surface to inside.Always there are some background signals in each quality place in SIMS, but this limited dynamic range.Ion counting to anion is also observed similar result.

Particle instance 19

Instance 19 is according to the method preparation of illustrative examples 1 and particle instance 8 to 10, and different is to have following modification.Silica gel particle is that the erose particle of granularity in 0.08mm to 0.6mm scope (can be available from AGM Container Controls, Inc., production code member: 920010).Particle is white, has 2.5% blue indicator.Before the DDMS steam treated, the particle that can directly use is exposed to dampness (30 ℉ and 80% relative humidity).During humidity exposure, the moisture of the part of per 10 to 20 minutes inspection particles increases, up to reaching 5.8 weight %.With the silica gel of about 940 gram humidity exposure pack into described in the particle instance 18 of inside of vacuum chamber than in the macroparticle agitator.Chamber evacuation is depressurized to 10 holders (1.3 * 10 ³Pa).Turn on agitator then stirs with the speed of 6rpm, and opens the DDMS valve to particle, to be used for steam treated.In first 10 minutes, constant pressure reaches 11 holders (1.5 * 10 ³Pa), consume 20.8 gram DDMS.Close the DDMS valve then, chamber was found time 2 minutes and is disposed to environmental condition.Take out particle samples and estimating then, have 20% particle floating with floating test.Again chamber evacuation is depressurized to 10 holders (1.3 * 10 ³Pa).Turn on agitator then stirs with the speed of 6rpm, and opened the DDMS valve 10 minutes to particle, to be used for steam treated.Constant pressure reaches 12.5 holders (1.7 * 10 ³Pa), consume 19.3 gram DDMS.Close the DDMS valve then, chamber was found time 2 minutes and is disposed to environmental condition.Take out particle samples and estimate, have 50% particle floating with floating test.Again chamber evacuation is depressurized to 10.5 holders (1.4 * 10 ³Pa).Turn on agitator then stirs with the speed of 6rpm, and opened the DDMS valve 10 minutes to particle, to be used for steam treated.Constant pressure reaches 15.6 holders (2.0 * 10 ³Pa), consume 17.2 gram DDMS.Close the DDMS valve then, chamber was found time 2 minutes and is disposed to environmental condition.Take out particle samples and estimate, have 95% particle floating with floating test.Stop after exposing 30 minutes altogether handling, consume 57.3 gram DDMS.Take out treated particle, sieve, and under 150 ℃, carry out 8 hours after drying, to remove the unreacted moisture that adsorbs in the particle.

Particle instance 20

Particle instance 20 is according to the method preparation of illustrative examples 1 and particle instance 8-10, and different is to have following modification.Silica gel particle is that the white irregularly shaped particle of granularity in 0.2mm to 1.0mm scope (can be available from International Silica Gel Co.LTD (Shandong, China)).Before the DDMS steam treated, the particle that can directly use is exposed to dampness (30 ℉ and 80% relative humidity).During humidity exposure, the moisture of the part of per 10 to 20 minutes inspection particles increases, up to reaching 6.0 weight %.The silica gel of about 1060 gram humidity exposure is packed in the particle agitator described in the particle instance 18 of inside of vacuum chamber.Chamber evacuation is depressurized to 10 holders (1.3 * 10 ³Pa).Turn on agitator then stirs with the speed of 12rpm, with being set to 0.7 mass flow controller as the DDMS valve.Opened the DDMS valve 32 minutes to particle, to be used for steam treated.Constant pressure reaches 12.5 holders (1.7 * 10 ³Pa), consume 32.6 gram DDMS.Close the DDMS valve then, chamber was found time 2 minutes and is disposed to environmental condition.Take out treated particle, under 150 ℃, carry out 8 hours after drying, to remove the unreacted moisture that adsorbs in the particle.Particle instance 20 has passed through the floating test described in the above-mentioned Test Methods section, has 100% treated particle from the teeth outwards floating.

Comparative example 2

With about 2 kilograms of silica gel (can be available from AGM Container Controls, Inc. (Tucson, AZ), production code member: 920014) with 1 liter/minute NF ₃Gas is handled under the pressure between 1 to 1.5 holder (130 to 200Pa).(can produce plasma with remote plasma source available from MKSInstruments (Wilmington, MA), model Astex-Astron eX).Before introducing gas, indoor pressure of foundation is lower than 0.1 holder (13Pa).Silica gel particle was handled 30 minutes.Let comparative example 2 stand the floating test described in the above-mentioned Test Methods section, different is that very small particles is sprayed onto in the bottle that water is housed.All particles are submerged all, and the reaction send " crack " sound.

The measurement of relative humidity

Make up the device 200 shown in Fig. 2 A and Fig. 2 B, with the actual condition of wearing of simulation absorbent article.This device is processed by two polycarbonate frame 202 that are of a size of 4 inches (10cm) * 8 inch (20cm).To be attached to underwear 204 (can trade name " NaturalFIT " available from Unicharm Corp.; Medium size; 87% cotton, 13% polyester) sanitary towel 206 is (can trade name " HADAOMOI " available from Unicharm Corp. (Minato-Ku, Tokyo; Japan)) place between the framework 202, sanitary towel 206 is exposed.Traceable formula araeometer/thermometer (temperature/humidity probe 216) (can be placed in the sanitary towel 206 available from Traceable Calibration Control company (Carrollton, TX), S/N 80174650), with the humidity in the measurement environment.The part sealing of the diaper chassis microporous membrane 208 of top frame 202 usefulness sanitary towels (can trade name " BODYFIT " available from Unicharm Corp.).The towel 210 of humidity is placed on the film, perspire with simulated skin.Cover whole device with polyethylene film 212 then.Hot compress pad 214 is placed on the top of device, open and regulate, thereby obtain 36 ℃ temperature.Device for opening then places 2 gram particles 205 at the middle part of sanitary towel 206.The device that closes, immediate record humidity, thereby the humidity when obtaining 0 minute.After 30 minutes, with syringe 1.5mL liquid 218 (Sanguis caprae seu ovis or saline solution) being expelled to away from the distance of probe 216 is the some place of 35mm.Sanguis caprae seu ovis is the mixture of BHI bacterial growth medium of Sanguis caprae seu ovis and the 60 volume % of 40 volume %, and both all derive from Biomerieux, and Inc. (Durham, NC).Per 30 minutes duplicate injection 1.5mL Sanguis caprae seu ovis or saline solution are estimated the persistent period to be shown in the following table.Probe 216 is connected to the personal computer with serial cable, uses relative humidity of software (can trade name " data collecting system " (DATAACQUISITION SYSTEM) available from Traceable Calibration Control company) monitoring in per 30 seconds then.Estimate and take out sanitary towel 206 when finishing, to be used for visual detection.

Absorbent article instance 1 to 4 and Comparative examples A

Estimate particle, the undressed silica gel of particle instance 1 to 4 and do not have the tester of particle with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 15.

Table 15

Absorbent article instance 5 to 8 and comparative example B

Estimate particle, the undressed silica gel of particle instance 1 to 3 and do not have the tester of particle with above-mentioned relative humidity method of testing; Different is to use with the sanitary towel of trade name " BODYFIT " available from Unicharm Corp., rather than " HADAOMOI " sanitary towel.The sanitary towel that silica gel particle is not set on it is used as tester.These sanitary towels do not contain SAP.Estimate the particle of 3 gram particle instances 1, rather than 2 grams.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 16.

Table 16

Absorbent article instance 9 and comparative example C

Estimate particle, undressed silica gel and the tester of particle instance 1 with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Evaluation time is long such as the evaluation time of the absorbent article instance 1 to 8 shown in last.The result is shown in the following table 17.In this table, " n.d. " representes undetermined.

Table 17

Absorbent article instance 10 to 12

With not commensurability particle instance 1 particle of above-mentioned relative humidity method of testing evaluation.The sanitary towel that silica gel particle is not set on it is used as tester.Amount with instance 1 particle shown in the following table 18 is estimated.The sodium chloride deionized water solution of saline solution, 0.9 weight % is used as the fluid of injection.The result is shown in the following table 18.

Table 18

Absorbent article instance 13 to 15

Estimate particle instance 1 particle of a plurality of positions in the sanitary towel with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Said position is under the paper pulp, just above the paper pulp and just below top flat.The sodium chloride deionized water solution of saline solution, 0.9 weight % is used as the fluid of injection.The result is shown in the following table 19.

Table 19

Absorbent article instance 16 to 18 and Comparative Example D

Estimate particle instance

1,5 and 6 particle, undressed silica gel and tester with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 20.

Table 20

Absorbent article instance 19 to 22 and Comparative Example E

Estimate particle, undressed silica gel and the tester of illustrative examples 1 and particle instance 8 to 10 with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 21.

Table 21

Absorbent article instance 23 to 25 and Comparative Example F

Estimate illustrative examples 2 and particle instance 11 and 12 particle, undressed silica gel and tester with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 22.

Table 22

Absorbent article instance 26 to 29 and comparative example G

Estimate particle, undressed silica gel and the tester of illustrative examples 4 and particle instance 13 to 15 with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 23.

Table 23

Absorbent article instance 30 to 32 and Comparative Example H

Estimate particle instance 12,15 and 7 particle, undressed silica gel and tester with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 24.

Table 24

Absorbent article instance 33 and 34 and Comparative Example I

Estimate particle instance 7 and 16 particle, undressed silica gel and tester with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 25.

Table 25

Absorbent article instance 35 to 40 and Comparative Example J

Estimate illustrative examples 5 to 8 and the particle of particle instance 16 and 17, undressed silica gel and tester with above-mentioned relative humidity method of testing.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 26.

Table 26

Absorbent article instance 41 and 42 and comparative example K

Estimate particle, undressed silica gel and the tester of particle instance 18 and comparative example 1 with above-mentioned relative humidity method of testing.Use with trade name " BODYFIT " available from Unicharm Corp. (Minato-Ku, Tokyo, sanitary towel Japan), rather than " HADAOMOI " sanitary towel.The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 27.

Table 27

Absorbent article instance 43 and 44 and comparative example L and M

Estimate particle instance 19 and 20 particle, undressed silica gel and tester with above-mentioned relative humidity method of testing.Use with trade name " BODYFIT " available from Unicharm Corp. (Minato-Ku, Tokyo, sanitary towel Japan), rather than " HADAOMOI " sanitary towel.The sanitary towel that silica gel particle is not set on it is used as tester.For comparative example L, undressed silica gel is the silica gel that is used to prepare particle instance 19.For comparative example M, undressed silica gel is the silica gel that is used to prepare particle instance 20.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 28.

Table 28

Absorbent article instance 45 and comparative example N

With above-mentioned relative humidity method of testing estimate particle instance 20 particle, be used to prepare the undressed silica gel and the tester of particle instance 20.Use with trade name " LAURIER F " available from Kao Corp. (Chuo-ku, Tokyo, Japan), paper pulp core zone comprises the sanitary towel of a large amount of SAP, rather than with the sanitary towel of trade name " HADAOMOI " available from Unicharm Corp..The sanitary towel that silica gel particle is not set on it is used as tester.Sanguis caprae seu ovis is the fluid of injection.The result is shown in the following table 29.

Table 29

Tea bag water absorbance

Some the water absorbability of treated porous granule that is used for following instance with this method of testing evaluation.Tea bag is processed by RIPSTOP, and the sieve aperture of this RIPSTOP is 57 microns (255 orders), from its downcut 2 inches (5.1cm) wide * 6 inches (15.2cm) long part and be folded into 2 inches (5.1cm) wide * 3 inches (7.6cm) long tea bag.Side heat seal with tea bag.Inside dimension is that 3 inches (7.6cm) long * 1.5 inches (3.8cm) are wide.Use following operation.Under room temperature (75 ℉, 24 ℃), deionized water (400mL) is placed cup.2 gram particles are placed tea bag.Tea bag is immersed in the deionization water tumbler, and kept 3 minutes.Take out tea bag and draining 1 minute.Measure the inner weight in wet base of the tea bag of particle that has.Tea bag with being unkitted particle repeats this operation, obtains the weight in wet base of tea bag.The tea bag and the empty tea bag of particle is equipped with in extruding in two four paper folding towel, weighs then, obtain " after the wiping " weight.Each sample all uses three parallel appearance.Confirm the water absorbability with following formula:

Water absorbability (g/g)=(be equipped with the wiping of tea bag of weight after the wiping of tea bag of particle-do not have particle after weight-drying particulate weight)/drying particulate weight.

The ammonia flavor is estimated

Some instance in the following instance is carried out the ammonia flavor to be estimated.At first treated or undressed active carbon or silica gel place vinyl cover (diameter is 2 inches) with 1 gram.The lid that particle will be housed then places 8 ounces glass jar.Add in the glass jar near inwall with the Ammonia of pipet, can not contact particle to guarantee solution with 5 milliliter of 0.1 weight %.Let particle absorb abnormal smells from the patient after 30 minutes, carry out the test of ammonia flavor with the Dreager pipe.Test dry-eye disease and wet sample respectively.Prepare wet sample as follows.1 gram drying particulate is placed above-mentioned tea bag.The tea bag that particle will be housed then immersed in the saline solution of 0.9 weight % 3 minutes.Pull out tea bag and draining 1 minute then, wipe the moisture that sticks between the particle away through the particle in the extruding tea bag between napkin.Sample after the collection wiping is used for the test of ammonia flavor with it as wet sample.

Particle instance 21 and 22

Particle instance 21 and the 22 method preparations according to illustrative examples 1 and particle instance 8-10, different is to have following modification.The silica gel particle of instance 21 is that the Type B silica gel particle of granularity in 1mm to 3mm scope (can be available from Toyota Kako Co.Ltd.; CAS number: 7631-86-9), the silica gel particle of instance 22 is the Type B silica gel particle of granularity in 0.5mm to 1.5mm scope (can available from International Silica Gel Co.Ltd).

Not to use glass tubing, but will be from the delivery of vapor of fluid supply to vacuum chamber with the rustless steel bubbler of electrobrightening.Bubbler is high cylindrical seal container, and its top has charging door, vapor space mouth and soaks the material mouth of pipe.Fill DDMS through charging door, and seal charging door with metal plug.Also be sealably coupled to the valve that soaks the material mouth with metal plug.In bubbler, fill after the DDMS, be closed to the valve and the charging door that soak the material pipe.Only the DDMS delivery of vapor is arrived vacuum chamber, to be used for reaction with the vapor space valve.Connect other valve, with the ON/OFF of control vapor source.Bubbler remains on ambient temperature (being 22-24 ℃).

Each the silica gel particle that will be used in the particle instance 21 and 22 (weight is illustrated in table 30) all is exposed to the steam in the humidity stove, absorbs the moisture of 6 weight % and 5 weight % respectively up to them.Pack into particle in the particle agitator then and place vacuum chamber.With rotary pump chamber evacuation is depressurized to indicated pressure, through close chamber's valve chamber and vacuum pump is broken off then.The initial weight of record DDMS container is opened the DDMS valve then, to handle particle.After the required processing time, the final weight of record DDMS container, and be recorded in the following table 30.Initial difference with final weight is designated as is used to handle the DDMS that particle consumes and measures.Before estimating, place baking oven dry down on treated particle in 150 ℃.

Table 30

Estimate and the evaluation methodology of tea bag water absorbance with above-mentioned floating test, aqueous water absorbance; Evaluation makes weight increase by the particle instance 21 and 22 and as the undressed silica gel of particle instance 21 and 22 raw material of 0.38 weight % and 2 weight % respectively through being exposed to dampness, and different is only to use one parallel kind in the evaluation of tea bag water absorbance.The result is summarised in the following table 31.

Table 31

Sample number into spectrum	Its floatability (%)	Water absorbance (g/2g)	Tea bag absorbance (g/g)
				Instance 21	>;90%	0.39	0.23
Instance 22	>;90%	1.10	0.64
				The undressed tester that is used for instance 21	0%	1.60	0.90
The undressed tester that is used for instance 22	0%	1.58	0.81

Absorb operation with above-mentioned steam and estimate particle instance 21 and 22 and, different is under 30 ℃ and 90% relative humidity measurement steam absorbance as the undressed silica gel of the raw material of particle instance 21.The result is shown in the following table 32.

Table 32

Sample number into spectrum	0.5 hour	1.0 hour	1.5 hour	2.0 hour	2.5 hour	3.0 hour
							Instance 21	0.26	0.36	0.44	0.56	0.66	0.72
Instance 22	0.36	0.50	0.60	0.70	0.74	0.78
							The undressed tester that is used for instance 21	0.52	0.76	0.96	1.16	1.32	1.48

With said method the treated particle of instance 22 is carried out ESCA.The depth section result shows, have the thick hydrophobic coating of 45nm on the external particles surface, and the inner surface in hole is undressed and hydrophilic basically.

Particle instance 23 to 24

The silica gel particle of handling in the instance 23 and 24 is that the Type B silica gel of granularity in 0.5mm to 1.5mm scope (can be available from International Silica Gel Co., Ltd.).Operation described in the embodiment 21 and 22, the different devices of roughly describing as among Fig. 3 C that are to use.The DDMS vapor pipe is furnished with nozzle 380.The external diameter of nozzle 380 is 0.5 inch (1.3cm), and the external diameter of DDMS vapor pipe is 0.25 inch (0.64cm).In the termination of the inside of nozzle 380, guarantee and hold open mode, last nozzle 380 is connected to the bottom of particle agitator through the polyethylene tube 382 of 0.25 inch (0.64cm).Through another mouthful nozzle 380 is connected to the outside steam of vacuum chamber and sends the source.Through water bubbler 368 nitrogen of flow velocity shown in the table 33 is bubbled, in nozzle 380, to produce source of water vapor.Also show other technological parameters in the following table 33.

Table 33

Particle instance 25

Like particle instance 22 said preparation particle instances 25, different be to use the process detail shown in the table 33.

Estimate and the evaluation methodology of tea bag water absorbance with above-mentioned floating test, aqueous water absorbance, evaluation makes weight increase by the particle instance 23-25 of 1.4 weight % and the undressed silica gel that is used as the raw material of particle instance 23-25 through being exposed to dampness.The result is summarised in the following table 34.

Table 34

Sample number into spectrum	Its floatability (%)	Water absorbance (g/2g)	Tea bag absorbance (g)
				Instance 23	>;90%	1.03	?0.48
Instance 24	>;90%	0.72	?0.22
				Instance 25	>;90%	1.15	?0.52
Undressed tester	0%	1.8	?0.9

Absorb that operation is estimated particle instance 23-25 and as the undressed silica gel of the raw material of particle instance 23-25 with above-mentioned steam, different is 30 ℃ with 90% relative humidity under measurement steam absorbance.The result is shown in the following table 35.

Table 35

Sample number into spectrum	0.5 hour	1.0 hour	1.5 hour	2.0 hour	2.5 hour	3.0 hour
							Instance 23	0.30	0.46	0.60	0.72	0.80	0.86
Instance 24	0.24	0.42	0.54	0.62	0.72	0.80
							Instance 25	0.24	0.42	0.56	0.66	0.76	0.82
Undressed tester	0.28	0.48	0.66	0.80	0.94	1.04

Estimate particle instance 23 and as the undressed silica gel of the raw material of particle instance 23-25 with above-mentioned ammonia flavor evaluation procedure.The step of the wet sample of in-service evaluation.The result is shown in the following table 36.

Table 36

Sample	Dry weight, g	Weight in wet base, g	Dreager pipe reading/ppm	The % loss of weight
					Instance 23	1.0123	2.9456	22	78
Undressed tester	1.0133	2.1303	22	78

Particle instance 26

The silica gel particle of handling in the particle instance 26 is that the Type B silica gel of granularity in 0.5mm to 1.5mm scope (can be available from International Silica Gel Co., Ltd.).The 50 gram silica gel that can directly use are packed into is used for the 200cc agitator of illustrative examples 1 and particle instance 8 to 10, and chamber evacuation is depressurized to 100 holders (1.3 * 10 ⁴Pa).Let the ethanol steam get in the chamber through steam orifice in the agitator at.After 10 minutes, from agitator, take out sample, and measure the ethanol content that absorbs with water balance.Ethanol content is 8.19%.55.2 grams are absorbed alcoholic acid silica gel in advance packed in the 200cc agitator, and once more chamber evacuation has been depressurized to 100 holders (1.3 * 10 ⁴Pa).Carry out DDMS with above-mentioned particle instance 23 and 24 described methods and handle, the different nitrogen flow rates that are to use 0.1 liter/minute.The DDMS weight that the processing post consumption falls is 5.6 grams.Draw off treated sample, and following dry 10 minutes at 150 ℃.Estimate and tea bag water absorbance evaluation methodology evaluation particle instance 26 with above-mentioned floating test, aqueous water absorbance.In floating test, 100% particle is floating in the sample.In the aqueous water absorbance was estimated, the water absorbance of calculating was 0.92g/2g.In tea bag water absorbance was estimated, the water absorbance of calculating was 0.37g/g.

Absorb operation with above-mentioned steam and estimate particle instance 26, different is 30 ℃ with 90% relative humidity under measurement steam absorbance.The result is shown in the following table 37.

Table 37

Sample number into spectrum	0.5 hour	1.0 hour	1.5 hour	2.0 hour	2.5 hour	3.0 hour
							Instance 26	0.21	0.31	0.38	0.49	0.59	0.68

Particle instance 27 and 28

For particle instance 27 and 28, use two kinds of different activity charcoal samples.For particle instance 27, active carbon has 12 * 20 orders, and (1.68mm * 0.85mm) distributes than coarsegrain, and for particle instance 28, active carbon has 30 * 70 orders (the less particle size distribution of 0.60mm * 0.21mm).Two kinds of carbon granule are all available from Kuraray Chemical Co.Ltd. (Japan).Step according to particle instance 23 and 24 prepares particle instance 27 and 28, and wherein technological parameter is shown in the following table 38.

Table 38

Estimate and the evaluation methodology of tea bag water absorbance with above-mentioned aqueous water absorbance, estimate particle instance 27 and 28 and the undressed active carbon that is used as the raw material of particle instance 27 and 28, different is that the evaluation of tea bag water absorbance only uses one parallel kind to accomplish.The result is summarised in the following table 39.

Table 39

Sample number into spectrum	Water absorbance (g/2g)	Tea bag test (g/g)
			The undressed tester that is used for instance 27	0.77	0.82
Instance 27	0.64	0.65
			The undressed tester that is used for instance 28	0.84	0.90
Instance 28	0.70	0.49

Absorb operation with above-mentioned steam and estimate particle instance 27 and 28 and, different is under 35 ℃ and 80% relative humidity measurement steam absorbance as the undressed active carbon of the raw material of particle instance 27 and 28.The result is shown in the following table 40.

Table 40

Sample number into spectrum	0.5 hour	1.0 hour	1.5 hour	2.0 hour	2.5 hour	3.0 hour
							The undressed tester that is used for instance 27	0.31	0.58	0.72	0.86	0.95	0.97
Instance 27	0.30	0.52	0.63	0.73	0.78	0.80
							The undressed tester that is used for instance 28	0.36	0.57	0.74	0.84	0.88	0.87
Instance 28	0.42	0.67	0.76	0.78	0.78	0.77

Estimate particle instance 28 and as the undressed active carbon of the raw material of particle instance 28 with above-mentioned ammonia flavor evaluation procedure.The step of in-service evaluation dry-eye disease and wet sample.The result is shown in the following table 41.

Table 41

All patents that this paper mentions and publication are all incorporated into way of reference in view of the above in full.Under the prerequisite that does not break away from the scope of the present disclosure and spirit, those skilled in the art can carry out various modifications and change to the disclosure, and should be appreciated that the disclosure should not be subject to exemplary embodiment as herein described undeservedly.

Claims

1. treated porous granule, it comprises outer surface and inner bore surface, the major part at least of the said outer surface of wherein said treated porous granule comprises hydrophobic group, and wherein said inner bore surface is undressed basically.

2. treated porous granule according to claim 1, wherein said hydrophobic group comprises at least one in the alkyl or aryl, wherein alkyl and aryl are randomly replaced by fluorine separately.

3. treated porous granule; It comprises outer surface and inner bore surface; At least a portion of the said outer surface of wherein said treated porous granule comprises hydrophobic group; Said hydrophobic group comprises at least one in the alkyl or aryl, and wherein said alkyl and aryl are replaced by fluorine, and wherein said inner bore surface is for part is hydrophilic at least.

4. according to the described treated porous granule of aforementioned each claim, wherein said hydrophobic group comprises siloxanes, and said siloxanes has alkyl, aryl or their combination.

5. according to the described treated porous granule of aforementioned each claim; Wherein said treated porous granule is the silica gel particle with outer surface; As confirming through the x-ray photoelectron power spectrum, the as many as 50 angstroms depth places of said outer surface have the silicon atom of maximum 5 atom %.

6. many particles, said a plurality of particles comprise according to the described treated porous granule of aforementioned each claim.

7. a plurality of particles according to claim 6; Wherein when said a plurality of particles being sprayed on the water surface when forming monolayer; Said a plurality of particles of at least 75% float on the said water surface, and said a plurality of particle absorbs the steam of its weight at least 20% after under 30 ℃ and 50% relative humidity, keeping 24 hours.

8. according to claim 6 or the described a plurality of particles of claim 7, wherein under 30 ℃ and 80% relative humidity, the steam absorbance of said a plurality of particles is at least 60% of the steam absorbance of a plurality of contrast particles of not comprising said hydrophobic group.

9. according to each the described a plurality of particles in claim 6 to the claim 8; Wherein be exposed to when liquid, aqueous when at least a portion of said a plurality of particles; Compare with a plurality of contrast particles that do not comprise said hydrophobic group, said a plurality of particles can reduce relative humidity to a greater degree.

10. according to each the described a plurality of particles in claim 6 to the claim 9, wherein said a plurality of particles do not contain particle basically, and wherein said outer surface and said inner bore surface are handled with hydrophobic group.

11. according to each the described a plurality of particles in claim 6 to the claim 10, it also comprises in undressed desiccant particles or the color indicator at least one.

12. according to each the described a plurality of particles in claim 6 to the claim 11, it also comprises absorbing particle or fiber, said absorbing particle or fiber comprise at least one in super-absorbent polymer, hydrophilic nonwoven cloth or the wood pulp.

13. an absorbent components, it comprises absorbing material and combining according to each the described a plurality of particles in claim 6 to the claim 12.

14. an absorbent article, it comprises the egative film of liquid permeable topsheet, liquid non-permeate and in absorbent components according to claim 13 between said top flat and said egative film or the described a plurality of particles of claim 12 at least one.

15. following particle is as the purposes of desiccant: according to each the described treated porous granule in claim 1 to the claim 5; Or according to each the described a plurality of particles in claim 6 to the claim 12.

16. following particle is as the purposes of odor control agent: according to each the described treated porous granule in claim 1 to the claim 5; Or according to each the described a plurality of particles in claim 6 to the claim 12.